JP2008239532A - Method for producing 3-phenoxy-4-pyridazinol derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a 3-phenoxy-4-pyridazinol derivative (I) having an excellent herbicidal activity. <P>SOLUTION: The method for producing a 3-phenoxy-4-pyridazinol derivative (I) comprises reacting a 3-phenoxypyridazine derivative with an oxidizing agent to give a mixture of a 3-phenoxypyridazine 1-oxide derivative (III) and a 3-phenoxypyridazine 2-oxide derivative (IV), then reacting the mixture with a halogenating agent to give a mixture of a 4-halogeno-3-phenoxypyridazine derivative (V) and the 2-oxide form (IV), then reacting the mixture with a reducing agent to give a mixture of the 4-halogeno form (V) and a 3-phenoxy form (II), then hydrolyzing the mixture under a basic condition and then subjecting the hydrolyzate to separating extraction with water and a water-immiscible organic solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a 3-phenoxy-4-pyridazinol derivative.

The 3-phenoxy-4-pyridazinol compound has an excellent herbicidal activity, and this compound oxidizes the 3-phenoxypyridazine compound to obtain 3-phenoxypyridazine 1-oxide compound and 3-phenoxypyridazine 2-oxide compound. Subsequently, it is known that this mixture is chlorinated to obtain a 4-chloro-3-phenoxypyridazine compound, and then produced by hydrolysis under basic conditions (Patent Document 1). ).
However, in the above production method, the regioselectivity of oxidation of the 3-phenoxypyridazine compound is generally low, and it is difficult to recover the 3-phenoxypyridazine 2-oxide compound generated as a by-product at that time. -It is not necessarily an efficient way to produce phenoxy-4-pyridazinol compounds.
Japanese Patent Laying-Open No. 2004-002263 (= WO 03/016286)

  In view of the importance of 3-phenoxy-4-pyridazinol derivatives having excellent herbicidal activity, the present inventors have conducted extensive studies to develop an efficient synthesis method. As a result, 3-phenoxypyridazine derivatives were used as starting materials. , Reaction with an oxidizing agent, reaction with a halogenating agent, reaction with a reducing agent and basic conditions, followed by hydrolysis reaction, followed by liquid separation extraction, from the aqueous layer, 3-phenoxy- A 3-phenoxy-4-pyridazinol can be separated from the water-immiscible organic layer by separating the 4-pyridazinol derivative and simultaneously recovering the 3-phenoxypyridazine derivative as a starting material and reusing the 3-phenoxypyridazine derivative. A method for producing a derivative was found and the present invention was completed.

  The present invention can produce a high-purity target product (3-phenoxy-4-pyridazinol derivative) with a simple operation and high yield, and can further reuse the starting material (3-phenoxypyridazine derivative). An object of the present invention is to provide a method for producing a 3-phenoxy-4-pyridazinol derivative.

［式中、Ｒ¹は、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆ハロアルキル基、Ｃ₃〜Ｃ₆シクロアルキル基、Ｃ₂〜Ｃ₆アルケニル基、シアノ基、Ｃ₂〜Ｃ₇アルキルカルボニル基、ジ（Ｃ₁〜Ｃ₆アルキル）カルバモイル基、置換されていてもよいフェニル基（当該置換基は、下記置換群Ａから選ばれる置換基である。）、５〜６員複素環基（当該複素環基は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有してもよい。）、Ｃ₁〜Ｃ₆アルコキシ基、置換されていてもよいフェノキシ基（当該置換基は、下記置換群Ａから選ばれる置換基である。）又は置換されていてもよい５〜６員複素環オキシ基｛当該複素環基は、環中に、１個の、窒素原子、酸素原子又は硫黄原子を含有し、更に１〜２個の窒素原子を含有していてもよく、当該置換基は、置換されていてもよいベンゾイル基（当該置換基は、下記置換群Ａから選ばれる置換基である。）及びＣ₁〜Ｃ₆アルキル基からなる群から選ばれる置換基である。｝を表し、 The present invention
General formula

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ -C ₆ alkenyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, di (C ₁ -C ₆ alkyl) carbamoyl group, optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), 5 -6-membered heterocyclic group (the heterocyclic group may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1-2 nitrogen atoms). C ₁ -C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a substituent selected from substituent group a.), or an optionally substituted 5- to 6-membered heterocyclic oxy group {The heterocyclic group contains one nitrogen atom, oxygen atom or sulfur atom in the ring. Further, it may further contain 1 to 2 nitrogen atoms, and the substituent is an optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A). And a substituent selected from the group consisting of C _{1 to} C ₆ alkyl groups. },

R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group, an optionally substituted benzoyl group (the substituent is the following substituent) A substituent selected from group A.), a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A), substitution An optionally substituted phenylthio group (the substituent is a substituent selected from the following substituent group A) or a tri (C ₁ -C ₆ alkyl) silicon group;

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is represented by the following substituent group B) A C ₂ -C ₆ alkenyl group which may be substituted (the substituent is a cyano group or a nitro group), a C ₂ -C ₆ alkynyl group, a substituted group. C ₃ -C ₆ cycloalkyl group (the substituent is a substituent selected from the following substituent group C), C ₄ -C ₁₀ bicycloalkyl group, cyano group, formyl group, C ₂ -C ₇ alkylcarbonyl group, optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A), carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, carbamoyl group, di ( C ₁ -C ₆ alkyl group) carbamoyl group, An optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), an optionally substituted 3- to 6-membered heterocyclic group (the heterocyclic ring is in the ring); 1 nitrogen atom, oxygen atom or sulfur atom, 1 to 2 nitrogen atoms may be further contained, and may be condensed with a benzene ring. A substituent selected from the group E.), an optionally substituted amino group (the substituent is a substituent selected from the following substituent group D), a nitro group, a hydroxyl group, C _{1 to} C _6. An alkoxy group, a C ₁ -C ₆ haloalkoxy group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a hydroxyl group or a halogen atom and a C _1- is pyridazinyloxy group substituted by a C ₆ alkoxy group ), An optionally substituted 5- to 6-membered heterocyclic oxy group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms) And the substituent is a substituent selected from the following substituent group E), and an optionally substituted benzoyloxy group (the substituent is a substituent selected from the following substituent group A) Group), an optionally substituted phenylsulfonyloxy group (the substituent is a substituent selected from the following substituent group A), a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkyl. Represents a sulfinyl group, a C ₁ -C ₆ alkylsulfonyl group or a tri (C ₁ -C ₆ alkyl) silicon group, or two adjacent ones of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ Are substituted together with the carbon atom to which each is attached. A 3- to 6-membered cyclic hydrocarbon group (the hydrocarbon group may be interrupted by the same or different 1-2 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, the substituents are halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a oxo group, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group If the C ₁ -C ₆ alkyl group is substituted, may form a new 3-membered ring with other C ₁ -C ₆ alkyl group or a carbon atom on the ring. )

Substituent group A is a group consisting of halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, a cyano group and a (C ₁ -C ₆ alkyl) silyl group And

Substituent group B, a halogen atom, C ₃ -C ₆ cycloalkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a phenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, consisting of C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₄ alkyl dioxy group, hydroxyimino group and C ₁ -C ₆ alkoxyimino group A group,

Substituent group C is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from the following substituent group B), C ₃ -C ₆ cycloalkyl group. , C ₂ -C ₆ alkenyl group, cyano group, C ₂ -C ₇ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₆ alkyl group) carbamoyl Group, an optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), a 5- to 6-membered heterocyclic group (the heterocyclic ring has one , A nitrogen atom, an oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms.), An optionally substituted amino group (the substituent is from the following substitution group D) Selected substituents), nitro groups, hydroxyl groups, ₁ -C ₆ alkoxy groups, C ₁ -C ₆ haloalkoxy group, a phenoxy group, C ₁ -C ₆ alkylthio group, Fenichio group, C ₁ -C ₆ alkylsulfinyl group consisting Le group and C ₁ -C ₆ alkylsulfonyl group And

Substituent group D is, C ₁ -C ₆ alkyl group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a di (C ₁ -C ₆ alkyl group) carbamoyl group and a C ₁ -C ₆ A group consisting of alkylsulfonyl groups,

Substituent group E includes a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a hydroxyl group, and an optionally substituted phenylsulfonyl group (the substituent is a substituent selected from the following substituent group A) Group) and di (C ₁ -C ₆ alkyl) sulfamoyl groups. ]
A process for producing a 3-phenoxy-4-pyridazinol derivative (I) represented by:

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は前記と同意義を表す。）
で表される３−フェノキシピリダジン誘導体（II）を酸化剤との反応に付し、一般式 General formula

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
A 3-phenoxypyridazine derivative (II) represented by the general formula

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は前記と同意義を表す。）
で表される３−フェノキシピリダジン １−オキシド誘導体（III）と、

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
3-phenoxypyridazine 1-oxide derivative (III) represented by:

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は前記と同意義を表す。）
で表される３−フェノキシピリダジン ２−オキシド誘導体（IV）との混合物を得て、 General formula

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
To obtain a mixture with 3-phenoxypyridazine 2-oxide derivative (IV) represented by:

（式中、Ｑは、ハロゲン原子を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、前記と同意義を表す。）
で表される４−ハロゲノ−３−フェノキシピリダジン誘導体（Ｖ）と３−フェノキシピリダジン ２−オキシド誘導体（IV）との混合物を得て、 Subsequently, this mixture is subjected to a reaction with a halogenating agent,
General formula

(In the formula, Q represents a halogen atom, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
To obtain a mixture of a 4-halogeno-3-phenoxypyridazine derivative (V) and a 3-phenoxypyridazine 2-oxide derivative (IV) represented by the formula:

Subsequently, this mixture is subjected to a reaction with a reducing agent,
A mixture of 4-halogeno-3-phenoxypyridazine derivative (V) and 3-phenoxypyridazine derivative (II) was obtained,

Subsequently, the mixture is subjected to a hydrolysis reaction under basic conditions.
Thereafter, if necessary, the solvent of the reaction mixture is distilled off, water and a water-immiscible organic solvent are added, liquid separation extraction is performed, and 3-phenoxy-4-pyridazinol derivative (I) is obtained from the aqueous layer. A method for producing a 3-phenoxy-4-pyridazinol derivative (I), characterized in that the 3-phenoxypyridazine derivative (II) is separated and simultaneously recovered from the water-immiscible organic layer,

  Furthermore, in addition to the above operation, the recovered 3-phenoxypyridazine derivative (II) is reacted with an oxidizing agent, a reaction with a halogenating agent, a reaction with a reducing agent and basic conditions in the same manner as described above. It is subjected to a hydrolysis reaction, followed by liquid separation extraction to separate the 3-phenoxy-4-pyridazinol derivative (I) from the aqueous layer, and at the same time, the 3-phenoxypyridazine derivative from the water-immiscible organic layer. The process for recovering (II) is further repeated at least once, and the recovered 3-phenoxypyridazine derivative (II) is reused. A method for producing the 3-phenoxy-4-pyridazinol derivative (I) It is.

  The production method of the present invention can produce a high-purity target product (3-phenoxy-4-pyridazinol derivative) with a simple operation and high yield, and further, a starting material (3-phenoxypyridazine derivative) can be produced. Since it can be reused, it is an industrially extremely advantageous production method for stably producing the 3-phenoxy-4-pyridazinol derivative (I) having excellent herbicidal activity at a low cost and in a high yield.

In the compound (I) and the like used in the production method of the present invention, the “halogen atom” such as R ¹ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or It is a bromine atom, more preferably a chlorine atom or a bromine atom, and even more preferably a chlorine atom.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ alkyl group” such as R ¹ is a linear or branched alkyl group having 1 to 6 carbon atoms. , Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl, hexyl, 4-methylpentyl, 3-methylpentyl, 2- Methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl or It is a 2-ethylbutyl group, preferably a straight or branched chain alkyl group having 1 to 4 carbon atoms (C ₁ -C ₄ alkyl group), more preferably The number 1 to 3 linear or branched alkyl group having a carbon (C ₁ -C ₃ alkyl group), even more preferably more, the number one or two alkyl groups (C ₁ -C ₂ alkyl group having a carbon And particularly preferably a methyl group.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ haloalkyl group” such as R ¹ is the same as or different from the above-mentioned “halogen atom” substituted by 1 to 5 “halogen atoms”. a C ₁ -C ₆ alkyl group ", for example, chloromethyl, Jikurorumechiru, trichloromethyl, 1-chloroethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 1-chloropropyl, 3-chloropropyl, 1-chlorobutyl 4-chlorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, fluorochloromethyl, bromomethyl, 1-bromoethyl, 2 A bromoethyl or iodomethyl group, preferably a fluorine atom, a chlorine atom and A 1-3 C ₁ substituent is substituted -C ₃ alkyl groups the same or different from selected from the group consisting of atom, more preferably the same one to three, fluorine atoms or chlorine A C ₁ -C ₂ alkyl group substituted by an atom, even more preferably a fluoromethyl, difluoromethyl, trifluoromethyl or 2,2,2-trifluoroethyl group, particularly preferably a trifluoromethyl group. It is a group.

In the compound (I) and the like used in the production method of the present invention, the “C ₃ -C ₆ cycloalkyl group” such as R ¹ is a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group, preferably cyclopropyl Or it is a cyclobutyl group, More preferably, it is a cyclopropyl group.

In the compound (I) and the like used in the production method of the present invention, the “C ₂ -C ₆ alkenyl group” such as R ¹ is a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, , Vinyl, 1-methylvinyl, allyl, 1-propenyl, 1-methyl-1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 2-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-ethyl-2-butenyl, 3-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 1- Ethyl-3-butenyl, 2-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 4-pen It may be a tenenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl group, preferably a straight chain having 2 to 4 carbon atoms. A chain or branched chain alkenyl group (C ₂ -C ₄ alkenyl group), more preferably a vinyl, 1-methylvinyl, allyl, 2-propenyl or 1-methyl-2-propenyl group, particularly preferred. Is an allyl group.

In the compound (I) and the like used in the production method of the present invention, the “C ₂ -C ₇ alkylcarbonyl group” such as R ¹ is a group in which the “C ₁ -C ₆ alkyl group” is bonded to the carbonyl group. For example, an acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl or heptanoyl group, and preferably a carbonyl group to which a linear or branched alkyl group having 1 to 4 carbon atoms is bonded. a (C ₂ -C ₅ alkylcarbonyl group), even more preferably more, straight-chain or branched-chain alkyl group is bonded to a carbonyl group having 1 to 3 carbon atoms (C ₂ -C ₄ alkylcarbonyl group) And particularly preferably an acetyl, propionyl, valeryl or pivaloyl group, and most preferably an acetyl group.

In the compound (I) and the like used in the production method of the present invention, the “di (C ₁ -C ₆ alkyl) carbamoyl group” such as R ¹ is the same or different two “C ₁ -C ₆ alkyl groups”. Is a carbamoyl group bonded to a nitrogen atom, and may be, for example, a dimethylcarbamoyl, methylethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl or dihexylcarbamoyl group. A carbamoyl group {di (C ₁ -C ₃ alkyl) carbamoyl group} to which _three linear or branched alkyl groups are bonded, more preferably a dimethylcarbamoyl group or a diethylcarbamoyl group, and even more preferably. Is a dimethylcarbamoyl group.

In the compound (I) and the like used in the production method of the present invention, the “tri (C ₁ -C ₆ alkyl) silicon group” such as the substituent group A is the same or different three “C ₁ -C _6”. `` Alkyl group '' is a group bonded to a silicon atom, and may be, for example, a trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethylisopropylsilyl, t-butyldimethylsilyl or trihexylsilyl group, preferably the same or different A group {tri (C ₁ -C ₃ alkyl) silicon group} in which a linear or branched alkyl group having 1 to 3 carbon atoms is bonded to a silicon atom, more preferably trimethylsilyl or dimethylisopropylsilyl And even more preferably a trimethylsilyl group.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted phenyl group (the substituent is a substituent selected from substituent group A)” such as R ¹ or the like. , The “halogen atom”, the “C ₁ -C ₆ alkyl group”, the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C _1)”. The same or different 1 to 5 substituents selected from the group consisting of “-C ₆ alkyl) silicon group” may be substituted, for example, phenyl, fluorophenyl, difluorophenyl, trifluorophenyl , Chlorophenyl, dichlorophenyl, trichlorophenyl, fluorochlorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethyl Phenyl, ethylphenyl, fluoro (methyl) phenyl, chloro (methyl) phenyl, bromo (methyl) phenyl, cyclopropylphenyl, cyclopropyl (fluoro) phenyl, chloro (cyclopropyl) phenyl, cyclopropyl (methyl) phenyl, (tri It is a fluoromethyl) phenyl or fluoro (trifluoromethyl) phenyl group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, the group consisting of "fluorine atom, a chlorine atom and a bromine atom A C ₁ -C ₃ alkyl group substituted by 1 to 3 identical or different substituents selected from: a C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silicon group 1 to 3 identical or different substituents selected from the group consisting of may be substituted phenyl groups More preferably, phenyl, chlorophenyl, methylphenyl, trifluorophenyl or cyanophenyl group.

In the compound (I) and the like used in the production method of the present invention, a “5- to 6-membered heterocyclic group such as R ¹ (the heterocyclic ring has one nitrogen atom, oxygen atom or sulfur atom in the ring). And may further contain 1 to 2 nitrogen atoms.) "Contains 1 nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and 1 to 2 nitrogen atoms. 5-6 membered heterocyclic group optionally containing atoms, for example, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, triazolyl, pyranyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl Or a triazinyl group, preferably a 5-membered heterocyclic group (the heterocyclic ring contains one nitrogen, oxygen or sulfur atom in the ring, or 2 Containing nitrogen atoms.) Or a pyridazinyl group, more preferably a furyl, thienyl, pyrazolyl or pyridazinyl group.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ alkoxy group” such as R ¹ is a linear or branched alkoxy group having 1 to 6 carbon atoms. , Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentoxy, isopentoxy, 2-methylbutoxy, neopentoxy, 1-ethylpropoxy, hexyloxy, 4-methylpentoxy, 3-methyl Pentoxy, 2-methylpentoxy, 1-methylpentoxy, 3,3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, It may be a 2,3-dimethylbutoxy or 2-ethylbutoxy group, and is preferably a linear or branched group having 1 to 3 carbon atoms. A branched alkoxy group (C ₁ -C ₃ alkoxy group), more preferably a methoxy or ethoxy group, and even more preferably a methoxy group.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted phenoxy group (the substituent is a substituent selected from substituent group A)” such as R ¹ is “. , The “halogen atom”, the “C ₁ -C ₆ alkyl group”, the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C _1)”. The same or different 1 to 5 substituents selected from the group consisting of “—C ₆ alkyl) silicon group” may be substituted, such as phenoxy, fluorophenoxy, difluorophenoxy, trifluorophenoxy , Chlorophenoxy, dichlorophenoxy, trichlorophenoxy, fluorochlorophenoxy, methylphenoxy, dimethylphenoxy, trimethylphenoxy, tetramethyl Tylphenoxy, pentamethylphenoxy, ethylphenoxy, fluoro (methyl) phenoxy, chloro (methyl) phenoxy, bromo (methyl) phenoxy, cyclopropylphenoxy, cyclopropyl (fluoro) phenoxy, chloro (cyclopropyl) phenoxy, cyclopropyl (methyl) ) phenoxy, (be a trifluoromethyl) phenoxy or fluoro (trifluoromethyl) phenoxy group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, a chlorine atom and A C ₁ -C ₃ alkyl group substituted with 1 to 3 identical or different substituents selected from the group consisting of bromine atoms ”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) same or different 1 selected from the group consisting of silicon group A three substituents which may be substituted phenoxy group, and more preferably, phenoxy, chlorophenoxy, methyl phenoxy, trifluoromethyl phenoxy or cyanophenoxy group.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted benzoyl group (the substituent is a substituent selected from substituent group A)” such as R ¹ is “. , The “halogen atom”, the “C ₁ -C ₆ alkyl group”, the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C _1)”. 1 to 5 substituents selected from the group consisting of “—C ₆ alkyl) silicon group” are optionally substituted benzoyl groups, such as benzoyl, fluorobenzoyl, difluorobenzoyl, trifluorobenzoyl , Chlorobenzoyl, dichlorobenzoyl, trichlorobenzoyl, fluorochlorobenzoyl, methylbenzoyl, dimethylbenzoyl, trimethylbenzoyl, tetramethyl Tylbenzoyl, pentamethylbenzoyl, ethylbenzoyl, fluoro (methyl) benzoyl, chloro (methyl) benzoyl, bromo (methyl) benzoyl, cyclopropylbenzoyl, cyclopropyl (fluoro) benzoyl, chloro (cyclopropyl) benzoyl, cyclopropyl (methyl) ) benzoyl, (be a trifluoromethyl) benzoyl or fluoro (trifluoromethyl) benzoyl group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, a chlorine atom and A C ₁ -C ₃ alkyl group substituted with 1 to 3 identical or different substituents selected from the group consisting of bromine atoms ”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) same or different 1 selected from the group consisting of silicon group A 3 substituents which may be substituted with a benzoyl group, more preferably benzoyl, chlorobenzoyl, dichlorobenzoyl, methyl benzoyl, trifluoperazine Robben benzoyl or cyanobenzoyl group.

In the preparation the compounds used in the method (I) or the like of the present invention, "substituted optionally 5-6 membered heterocyclic group {said heterocyclic may be of such R ¹ is in the ring, the one, nitrogen It contains an atom, oxygen atom or sulfur atom, and may further contain 1 to 2 nitrogen atoms, and the substituent is an optionally substituted benzoyl group (the substituent is substituent group A). Is optionally substituted with a substituent selected from the group consisting of C _{1 to} C ₆ alkyl groups.} ”Is the above-mentioned“ optionally substituted benzoyl group (the substitution The group is a substituent selected from the substituent group A.) ”and the same or different 1 to 3 substituents selected from the group consisting of the“ C ₁ -C ₆ alkyl group ”. The “5- to 6-membered heterocyclic group (the heterocyclic ring is in the ring, Group containing a nitrogen atom, an oxygen atom or a sulfur atom, and further containing 1 or 2 nitrogen atoms.) ”, Preferably a fluorine atom, Chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, “C ₁ -C ₃ alkyl substituted with ₁ to ₃ identical or different substituents selected from the group consisting of fluorine atom, chlorine atom and bromine atom The same or different 1 to 3 substituents selected from the group consisting of “group”, C ₃ -C ₄ cycloalkyl group, cyano group and tri (C ₁ -C ₃ alkyl) silicon group may be substituted. Substituted with the same two C ₁ -C ₃ alkyl groups, “containing one nitrogen atom, oxygen atom or sulfur atom as a hetero atom, and one nitrogen atom A 5-membered heterocyclic oxy group which may be contained "and more The suitable is a two one-pyrazolyloxy group substituted by a benzoyl group and two C ₁ -C ₂ alkyl group substituted by a chlorine atom.

In the compound (I) and the like used in the production method of the present invention, “(C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group” such as R ² represents one of the above “C ₁ -C ₆ alkoxy”. is said that group "is substituted" C ₁ -C ₆ alkyl group ", for example, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, s- butoxymethyl, t-butoxymethyl, pentyloxymethyl, hexyloxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, methoxybutyl, be a methoxy pentyl or methoxy hexyl group, preferably a, C ₁ 1 amino C ₁ -C ₃ alkoxy group substituted -C ₆ An alkyl group, more preferably a methoxyethyl, ethoxyethyl or ethoxymethyl group.

In the compound (I) and the like used in the production method of the present invention, the “C ₂ -C ₇ alkoxycarbonyl group” such as R ² is a group in which the “C ₁ -C ₆ alkoxy group” is bonded to a carbonyl group. For example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, s-butoxycarbonyl, t-butoxycarbonyl, pentoxycarbonyl, isopentoxycarbonyl, 2-methylbutoxycarbonyl, neo Pentoxycarbonyl, 1-ethylpropoxycarbonyl, hexyloxycarbonyl, 4-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 1-methylpentoxycarbonyl, 3,3-dimethylbuto With a cicarbonyl, 2,2-dimethylbutoxycarbonyl, 1,1-dimethylbutoxycarbonyl, 1,2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl or 2-ethylbutoxycarbonyl group There resulting, preferably, a C ₁ -C ₃ group an alkoxy group is bonded to a carbonyl group (C ₂ -C ₄ alkoxycarbonyl group), more preferably a methoxycarbonyl or ethoxycarbonyl group, still more A methoxycarbonyl group is preferred.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted phenylthio group (the substituent is a substituent selected from Substituent Group A)” such as R ² . , The “halogen atom”, the “C ₁ -C ₆ alkyl group”, the “C ₁ -C ₆ haloalkyl group”, the “C ₃ -C ₆ cycloalkyl group”, the cyano group and the “tri (C _1)”. 1 to 5 substituents selected from the group consisting of “—C ₆ alkyl) silicon group” are optionally substituted phenylthio groups, for example, phenylthio, fluorophenylthio, difluorophenylthio, tri Fluorophenylthio, chlorophenylthio, dichlorophenylthio, trichlorophenylthio, fluorochlorophenylthio, methylphenylthio, dimethylphenylthio, trim Tilphenylthio, tetramethylphenylthio, pentamethylphenylthio, ethylphenylthio, fluoro (methyl) phenylthio, chloro (methyl) phenylthio, bromo (methyl) phenylthio, cyclopropylphenylthio, cyclopropyl (fluoro) phenylthio, chloro ( Cyclopropyl) phenylthio, cyclopropyl (methyl) phenylthio, (trifluoromethyl) phenylthio or fluoro (trifluoromethyl) phenylthio groups, preferably fluorine, chlorine, bromine, C ₁ -C ₃ alkyl A group, “C ₁ -C ₃ alkyl group substituted by 1 to 3 identical or different substituents selected from the group consisting of fluorine atom, chlorine atom and bromine atom”, C ₃ -C ₄ cycloalkyl group, cyano group and a tri (C ₁ -C ₃ alkyl The same or different 1 to 3 substituents selected from the group consisting of silicon groups are optionally substituted phenylthio groups, more preferably phenylthio, chlorophenylthio, methylphenylthio, trifluorophenylthio or It is a cyanophenylthio group.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ alkylthio group” of the substituent group B and the like is a linear or branched alkylthio group having 1 to 6 carbon atoms. For example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, s-butylthio, t-butylthio, pentylthio, isopentylthio, 2-methylbutylthio, neopentylthio, 1-ethylpropylthio, hexylthio, 4 -Methylpentylthio, 3-methylpentylthio, 2-methylpentylthio, 1-methylpentylthio, 3,3-dimethylbutylthio, 2,2-dimethylbutylthio, 1,1-dimethylbutylthio, 1,2 -Dimethylbutylthio, 1,3-dimethylbutylthio, 2,3-dimethylbutylthio or 2-ethyl It is a Chiruchio group, preferably a straight-chain or branched alkylthio group having 1 to 3 carbon atoms (C ₁ -C ₃ alkylthio group), more preferably a methylthio or ethylthio group, further More preferably, it is a methylthio group.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ alkylsulfinyl group” such as the substituent group B is a linear or branched alkylsulfinyl group having 1 to 6 carbon atoms. For example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, s-butylsulfinyl, t-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, 2-methylbutylsulfinyl, neopentylsulfinyl, 1 -Ethylpropylsulfinyl, hexylsulfinyl, 4-methylpentylsulfinyl, 3-methylpentylsulfinyl, 2-methylpentylsulfinyl, 1-methylpentylsulfinyl, 3,3-dimethylbutyl Rufinyl, 2,2-dimethylbutylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl or 2-ethylbutylsulfinyl group the resulting, preferably a straight or branched chain alkylsulfinyl group having 1 to 3 carbon atoms (C ₁ -C ₃ alkylsulfinyl group), more preferably a methylsulfinyl or ethylsulfinyl group, still More preferably, it is a methylsulfinyl group.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ alkylsulfonyl group” of the substituent group B and the like is a linear or branched alkylsulfonyl group having 1 to 6 carbon atoms. Yes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, s-butylsulfonyl, t-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, 2-methylbutylsulfonyl, neopentylsulfonyl, 1 -Ethylpropylsulfonyl, hexylsulfonyl, 4-methylpentylsulfonyl, 3-methylpentylsulfonyl, 2-methylpentylsulfonyl, 1-methylpentylsulfonyl, 3,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfone , 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl or 2-ethylbutylsulfonyl group, preferably a carbon number a 1-3 straight-chain or branched-chain alkylsulfonyl group (C ₁ -C ₃ alkylsulfonyl group), more preferably a methylsulfonyl or ethylsulfonyl group, further preferably more, methylsulfonyl group It is.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₄ alkylenedioxy group” such as the substituent group B is a linear or branched alkylenedioxy group having 1 to 4 carbon atoms. A group such as methylenedioxy, ethylenedioxy, propylenedioxy, trimethylenedioxy or tetramethylenedioxy group, preferably an alkylenedioxy group having 1 to 2 carbon atoms, More preferably, it is a 1,2-ethylenedioxy group.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ alkoxyimino group” of the substituent group B and the like is a linear or branched alkoxyimino group having 1 to 6 carbon atoms. Yes, for example, methoxyimino, ethoxyimino, propoxyimino, isopropoxyimino, butoxyimino, isobutoxyimino, s-butoxyimino, t-butoxyimino, pentoxyimino, isopentoxyimino, 2-methylbutoxyimino, neopentoxy Imino, 1-ethylpropoxyimino, hexyloxyimino, 4-methylpentoxyimino, 3-methylpentoxyimino, 2-methylpentoxyimino, 1-methylpentoxyimino, 3,3-dimethylbutoxyimino, 2, 2-dimethylbutoxyimino, 1,1-dimethylbutoxyimino, 1 It may be a 2-dimethylbutoxyimino, 1,3-dimethylbutoxyimino, 2,3-dimethylbutoxyimino or 2-ethylbutoxyimino group, preferably a linear or branched alkoxy having 1 to 3 carbon atoms An imino group (C ₁ -C ₃ alkoxyimino group), more preferably a methoxyimino or ethoxyimino group, and even more preferably a methoxyimino group.

In the compound (I) and the like used in the production method of the present invention, “an optionally substituted C ₁ -C ₆ alkyl group such as R ³ (the substituent is a substituent selected from the substituent group B). ) ", the" halogen atom "or the" C ₃ -C ₆ cycloalkyl group ", a cyano group, wherein" C ₂ -C ₇ alkylcarbonyl group ", the" C ₂ -C ₇ alkoxycarbonyl group " , A phenyl group, the “C ₁ -C ₆ alkoxy group”, the “C ₁ -C ₆ alkylthio group”, the “C ₁ -C ₆ alkylsulfinyl group”, the “C ₁ -C ₆ alkylsulfonyl group”, The “C ₁ -C ₄ alkylenedioxy group”, the hydroxyimino group or the “C ₁ -C ₆ alkoxyimino group” optionally substituted by the “C ₁ -C ₆ alkyl group”, for example, Fluoromethyl, difluo Methyl, trifluoromethyl, 2,2,2-trichloroethyl, cyclopropylmethyl, cyanomethyl, acetylmethyl, acetylethyl, methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, benzyl, methoxymethyl, methoxyethyl , Ethoxymethyl, ethoxyethyl, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, methylsulfinylmethyl, methylsulfonylmethyl, 2- (1,3-dioxolanyl), hydroxyiminomethyl or methoxyiminomethyl group preferably, fluorine atom, the same selected from the group consisting of chlorine atom and bromine atom or different 1 to 3 substituents are substituted C ₁ -C ₃ alkyl group, or, C ₃ -C ₄ cycloalkyl Alkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, a phenyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ alkylsulfinyl group, a C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₂ alkylenedioxy group, hydroxyimino group or C ₁ -C ₃ may be alkoxyimino groups substituted C ₁ -C ₃ alkyl group, More preferably, the same 1 to 3 C ₁ -C ₂ alkyl groups substituted with fluorine atoms or chlorine atoms, or cyclopropyl group, cyano group, C ₂ -C ₃ alkylcarbonyl group, C _2- C ₃ alkoxycarbonyl group, a phenyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ alkylthio group, C ₁ -C ₂ alkylsulfinyl group, C ₁ -C ₂ alkylsulfonyl group, Echirenjioki Ci group, hydroxyimino group or C ₁ -C ₂ alkoxyimino group optionally substituted C ₁ -C ₂ alkyl group, particularly preferably methyl, ethyl, isopropyl, trifluoromethyl or cyclopropylmethyl It is a group.

In the compound (I) and the like used in the production method of the present invention, “substituted C ₂ -C ₆ alkenyl group (the substituent is a cyano group or a nitro group)” such as R ³ is a cyano group. Or a “C ₂ -C ₆ alkenyl group” substituted with a nitro group, preferably a C ₂ -C ₃ alkenyl group substituted with a cyano group or a nitro group, more preferably cyanovinyl or Nitrovinyl group.

In the compound (I) and the like used in the production method of the present invention, the “C ₂ -C ₆ alkynyl group” such as R ³ is a linear or branched alkynyl group having 2 to 6 carbon atoms, for example, Ethynyl, 2-propynyl, 1-methyl-2-propynyl, 1-ethyl-2-propynyl, 2-butynyl, 1-methyl-2-butynyl, 1-ethyl-2-butynyl, 3-butynyl, 1-methyl- 3-butynyl, 2-methyl-3-butynyl, 1-ethyl-3-butynyl, 2-pentynyl, 1-methyl-2-pentynyl, 1-ethyl-2-pentynyl, 3-pentynyl, 1-methyl-3- Pentynyl, 2-methyl-3-pentynyl, 4-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl or 5-hexyl Preferably a straight-chain or branched alkynyl group having 3 to 4 carbon atoms (C ₃ -C ₄ alkynyl group), more preferably ethynyl, 1-propynyl or 2-propynyl. It is a group.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted amino group such as substituent group C (the substituent is a substituent selected from substituent group D)”. Is the above-mentioned “C ₁ -C ₆ alkyl group”, the above “C ₂ -C ₇ alkylcarbonyl group”, the above “C ₂ -C ₇ alkoxycarbonyl group”, the above “di (C ₁ -C ₆ alkyl) carbamoyl”. Group ”and an amino group which may be substituted by the same or different 1 to 2 substituents selected from the group consisting of the above-mentioned“ C ₁ -C ₆ alkylsulfonyl group ”, such as amino, methylamino, Ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, s-butylamino, t-butylamino, pentylamino, isopentylamino, (2-methylbutyl) amino, Neopentylamino, (1-ethylpropyl) amino, hexylamino, (4-methylpentyl) amino, (3-methylpentyl) amino, (2-methylpentyl) amino, (1-methylpentyl) amino, (3, 3-dimethylbutyl) amino, (2,2-dimethylbutyl) amino, (1,1-dimethylbutyl) amino, (1,2-dimethylbutyl) amino, (1,3-dimethylbutyl) amino, (2, 3-dimethylbutyl) amino, (2-ethylbutyl) amino, dimethylamino, (methyl) (ethyl) amino, diethylamino, dipropylamino, (methyl) (isopropyl) amino, diisopropylamino, dibutylamino, diisobutylamino, dis -Butylamino, di-t-butylamino, dipentylamino, diisopentylamino Di (2-methylbutyl) amino, dineopentylamino, di (1-ethylpropyl) amino, dihexylamino, di (4-methylpentyl) amino, di (3-methylpentyl) amino, di (2-methylpentyl) Amino, di (1-methylpentyl) amino, di (3,3-dimethylbutyl) amino, di (2,2-dimethylbutyl) amino, di (1,1-dimethylbutyl) amino, di (1,2- Dimethylbutyl) amino, di (1,3-dimethylbutyl) amino, di (2,3-dimethylbutyl) amino, di (2-ethylbutyl) amino, acetylamino, propionylamino, butanoylamino, (2-methylpropaline) Noyl) amino, pentanoylamino, (2,2-dimethylpropanoyl) amino, (2,2-dimethylpentanoyl) amino, 2-methylbutanoyl) amino, (3-methylbutanoyl) amino, hexanoylamino, heptanoylamino, (3,3-dimethylbutanoyl) amino, methoxycarbonylamino, ethoxycarbonylamino, propoxycarbonylamino, isopropoxy Carbonylamino, butoxycarbonylamino, isobutoxycarbonylamino, s-butoxycarbonylamino, t-butoxycarbonylamino, pentoxycarbonylamino, isopentoxycarbonylamino, (2-methylbutoxycarbonyl) amino, neopentoxycarbonylamino, (1-ethylpropoxycarbonyl) amino, hexyloxycarbonylamino, (4-methylpentoxycarbonyl) amino, (3-methylpentoxycarbonyl) amino, (2-methyl Tilpentoxycarbonyl) amino, (1-methylpentoxycarbonyl) amino, (3,3-dimethylbutoxycarbonyl) amino, (2,2-dimethylbutoxycarbonyl) amino, (1,1-dimethylbutoxycarbonyl) amino, (1,2-dimethylbutoxycarbonyl) amino, (1,3-dimethylbutoxycarbonyl) amino, (2,3-dimethylbutoxycarbonyl) amino, (2-ethylbutoxycarbonyl) amino, dimethylcarbamoylamino, (methylethylcarbamoyl) ) Amino, diethylcarbamoylamino, dipropylcarbamoylamino, dibutylcarbamoylamino, dihexylcarbamoylamino, methylsulfonylamino, ethylsulfonylamino, propylsulfonylamino, isopropylsulfoni Amino, butylsulfonyl amino, t- butyl sulfonylamino, or hexyl sulfonylamino obtained, preferably the same or different 1-2 C ₁ -C ₃ alkyl group, or, C ₂ -C ₄ alkylcarbonyl group a C ₂ -C ₄ alkoxycarbonyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group or a C ₁ -C ₃ alkylsulfonyl amino group which may be substituted by a group, more preferably, amino, methyl Amino, ethylamino, dimethylamino, diethylamino, acetylamino, propionylamino, (2-methylpropanoyl) amino, (2,2-dimethylpropanoyl) amino, methoxycarbonylamino, ethoxycarbonylamino, dimethylcarbamoylamino, diethylcarbamoyl Amino, methylsulfonylamino or An ethylsulfonylamino group, particularly preferably a dimethylamino group.

In the compound (I) and the like used in the production method of the present invention, the “C ₁ -C ₆ haloalkoxy group” in the substituent group C and the like is substituted with 1 to 5 “halogen atoms” which are the same or different. Examples of the “C ₁ -C ₆ alkoxy group” include, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, 1-chloroethoxy, 2-chloroethoxy, 2,2,2-trichloroethoxy, 1-chloropropoxy, 3 -Chloropropoxy, 1-chlorobutoxy, 4-chlorobutoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, fluorochloro Methoxy, bromomethoxy, 1-bromoethoxy, 2-bromoethoxy or iodome A C ₁ -C ₃ alkoxy group substituted with 1 to 3 identical or different substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom; Preferred are the same 1 to 3 C ₁ -C ₂ alkoxy groups substituted with fluorine atoms or chlorine atoms, and even more preferred are fluoromethoxy, difluoromethoxy, trifluoromethoxy or 2,2, A 2-trichloroethoxy group, particularly preferably a trifluoromethoxy group.

In the compound (I) and the like used in the production method of the present invention, “an optionally substituted C ₃ -C ₆ cycloalkyl group such as R ³ (the substituent is a substituent selected from the substituent group C) “Is a halogen atom”, “the C ₁ -C ₆ alkyl group which may be substituted (the substituent is a substituent selected from substituent group B)”, “C ₃ -C ₆ cycloalkyl group”, “C ₂ -C ₆ alkenyl group”, cyano group, “C ₂ -C ₇ alkylcarbonyl group”, benzoyl group, carboxyl group, “C ₂ -C ₇ alkoxy group” “Carbonyl group”, carbamoyl group, “di (C ₁ -C ₆ alkyl) carbamoyl group”, “optionally substituted phenyl group (the substituent is a substituent selected from substituent group A). ) ”,“ 5- to 6-membered heterocyclic group ( The heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1 or 2 nitrogen atoms. amino group which may (the substituent is a substituent selected from substituent group D.) ", a nitro group, a hydroxyl group, the" C ₁ -C ₆ alkoxy group ", the" C ₁ -C ₆ haloalkoxy The same group selected from the group consisting of “group”, phenoxy group, “C ₁ -C ₆ alkylthio group”, phenylthio group, “C ₁ -C ₆ alkylsulfinyl group” and “C ₁ -C ₆ alkylsulfonyl group”. or different said that may be substituted by 1 to 5 substituents a "C ₃ -C ₆ cycloalkyl group", for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluoro cyclopropyl, Jifuruoroshi Ropropyl, chlorocyclopropyl, dichlorocyclopropyl, bromocyclopropyl, dibromocyclopropyl, iodocyclopropyl, methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, isopropylcyclopropyl, butylcyclopropyl, t-butylcyclopropyl, hexylcyclo Propyl, cyclopropylcyclopropyl, cyclobutylcyclopropyl, cyclopentylcyclopropyl, (fluoromethyl) cyclopropyl, (chloromethyl) cyclopropyl, (bromomethyl) cyclopropyl, (difluoromethyl) cyclopropyl, (trifluoromethyl) cyclopropyl , (Trichloromethyl) cyclopropyl, (2,2,2-trifluoroethyl) cyclopropyl, (2,2,2-trichloro Til) cyclopropyl, vinylcyclopropyl, (methoxymethyl) cyclopropyl, (ethoxymethyl) cyclopropyl, (isopropoxymethyl) cyclopropyl, (methylthiomethyl) cyclopropyl, (ethylthiomethyl) cyclopropyl, (isopropylthiomethyl) ) Cyclopropyl, (methylsulfinylmethyl) cyclopropyl, (ethylsulfinylmethyl) cyclopropyl, (methylsulfonylmethyl) cyclopropyl, (ethylsulfonylmethyl) cyclopropyl, cyanocyclopropyl, (1-methoxyiminoethyl) cyclopropyl, Acetylcyclopropyl, propionylcyclopropyl, benzoylcyclopropyl, carboxylcyclopropyl, methoxycarbonylcyclopropyl, ethoxycarbonyl Ropropyl, carbamoylcyclopropyl, (dimethylcarbamoyl) cyclopropyl, (diethylcarbamoyl) cyclopropyl, phenylcyclopropyl, (fluorophenyl) cyclopropyl, (chlorophenyl) cyclopropyl, tolylcyclopropyl, furylcyclopropyl, thienylcyclopropyl, pyridyl Cyclopropyl, aminocyclopropyl, (methylamino) cyclopropyl, (dimethylamino) cyclopropyl, (acetylamino) cyclopropyl, (methoxycarbonylamino) cyclopropyl, (3,3-dimethylureido) cyclopropyl, (methylsulfonyl) Amino) cyclopropyl, nitrocyclopropyl, hydroxycyclopropyl, methoxycyclopropyl, ethoxycyclopropyl, (trifluoro) Methoxy) cyclopropyl, phenoxycyclopropyl, methylthiocyclopropyl, ethylthiocyclopropyl, phenylthiocyclopropyl, methylsulfinylcyclopropyl, ethylsulfinylcyclopropyl, methylsulfonylcyclopropyl, ethylsulfonylcyclopropyl, dimethylcyclopropyl, methyl (ethyl ) Cyclopropyl, diethylcyclopropyl, biscyanocyclopropyl, trimethylcyclopropyl, tetramethylcyclopropyl, pentamethylcyclopropyl, methylcyclobutyl, vinylcyclobutyl, cyanocyclobutyl, carboxylcyclobutyl, acetylcyclobutyl, methoxycarbonylcyclo It can be a butyl or aminocyclobutyl group, preferably a fluorine atom, a chlorine atom, a bromine atom C ₁ -C ₃ alkyl group, C ₃ -C ₄ same or different 1 to 5 substituents selected from the group consisting of cycloalkyl group and a cyano group, or, consists of a "fluorine atom, a chlorine atom and a bromine atom C ₁ -C ₃ alkyl group one to three substituents the same or different from selected from the group is substituted, or, C ₃ -C ₄ cycloalkyl group, a cyano group, C ₂ -C ₄ alkylcarbonyl group, C ₂ -C ₄ alkoxycarbonyl group, a phenyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ alkylthio group, C ₁ -C ₃ alkylsulfinyl group, C ₁ -C ₃ alkylsulfonyl groups, C ₁ -C ₂ alkylenedioxy group, hydroxyimino C ₁ -C ₃ alkyl group which groups or C ₁ -C ₃ alkoxyimino group is substituted ", C ₂ -C ₄ alkenyl group, C ₂ -C ₄ alkylcarbonyl group, a benzoyl group, Carbo Xyl group, C ₂ -C ₄ alkoxycarbonyl group, carbamoyl group, di (C ₁ -C ₃ alkyl) carbamoyl group, “fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, (fluorine atom, chlorine A C ₁ -C ₃ alkyl group substituted with 1 to 3 identical or different substituents selected from the group consisting of an atom and a bromine atom), a C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) same or different 1 to 3 substituents are substituted phenyl groups optionally have "5-membered Hajime Tamaki (said heterocyclic ring selected from the group consisting of silicon group in the ring, Contains one nitrogen, oxygen or sulfur atom. ), “One or two identical or different C ₁ -C ₃ alkyl groups, or C ₂ -C ₄ alkylcarbonyl groups, C ₂ -C ₄ alkoxycarbonyl groups, di (C ₁ -C ₃ alkyl) carbamoyl group or C ₁ -C ₃ alkylsulfonyl amino group which may be substituted by a group ", a nitro group, a hydroxyl group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group, a phenoxy group, C ₁ -C ₃ alkylthio group, a phenylthio group, C ₁ -C ₃ alkylsulfinyl group or a C ₁ -C ₃ alkylsulfonyl groups by an optionally substituted C ₃ -C ₄ even though cycloalkyl group, more preferably, a chlorine atom, a bromine atom , C ₁ -C ₂ alkyl group, the same or different 1 to 3 substituents selected from the group consisting of cyclopropyl group and cyano group, or, selected from the group consisting of "a chlorine atom and a bromine atom C ₁ -C ₂ alkyl group same 1 to 3 substituents were substitutions, or a cyclopropyl group, a cyano group, C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, a phenyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ alkylthio group, C ₁ -C ₂ alkylsulfinyl group, C ₁ -C ₂ alkylsulfonyl group, 1,2-ethylenedioxy group, hydroxyimino group or a C ₁ -C ₂ alkoxyimino group C ₁ -C ₂ alkyl group "which is substituted, C ₂ -C ₃ alkenyl group, C ₂ -C ₃ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₃ alkoxycarbonyl group , carbamoyl group, di (C ₁ -C ₂ alkyl) carbamoyl group, "a chlorine atom, a bromine atom, C ₁ -C ₂ alkyl group, (identical one to three, fluorine atoms or chlorine atoms are substituted ₁ -C ₂ alkyl group), a cyclopropyl group, the same or different 1 to 2 substituents selected from cyano group and a tri (C ₁ -C ₂ alkyl) group consisting of silicon group may be substituted by Phenyl group ”, furyl group, thienyl group,“ the same 1-2 C ₁ -C ₂ alkyl group, or C ₂ -C ₃ alkylcarbonyl group, C ₂ -C ₃ alkoxycarbonyl group, di (C ₁ -C ₂ alkyl) carbamoyl group or a C ₁ -C ₂ alkylsulfonyl amino group which may be substituted by a group ", a nitro group, a hydroxyl group, C ₁ -C ₂ alkoxy group, C ₁ -C ₂ haloalkoxy group, a phenoxy group, C ₁ -C ₂ alkylthio group, a phenylthio group, C ₁ -C ₂ alkylsulfinyl group or C ₁ -C ₂ alkylsulfonyl optionally cyclopropyl optionally substituted by a group group or Shikurobu And particularly preferably cyclopropyl, fluorocyclopropyl, difluorocyclopropyl, chlorocyclopropyl, dichlorocyclopropyl, fluorochlorocyclopropyl, dibromocyclopropyl, methylcyclopropyl, dimethylcyclopropyl, ethylcyclopropyl, Cyclopropylcyclopropyl, methoxycyclopropyl, ethoxycyclopropyl, (methoxymethyl) cyclopropyl or cyclobutyl groups.

In the compound (I) and the like used in the production method of the present invention, “C ₄ -C ₁₀ bicycloalkyl group” such as R ³ is a bicyclic hydrocarbon having 4 to 10 carbon atoms. It may be a butyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl or bicyclodecyl group, preferably a bicyclohexyl or bicycloheptyl group, more preferably a bicyclo [3.1.0]. It is a hexyl or bicyclo [4.1.0] heptyl group, and more preferably a bicyclo [3.1.0] hexan-6-yl group.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted phenylsulfonyl group such as substituent group E (the substituent is a substituent selected from substituent group A). ) ”Is the above“ halogen atom ”, the above“ C ₁ -C ₆ alkyl group ”, the above“ C ₁ -C ₆ haloalkyl group ”, the above“ C ₃ -C ₆ cycloalkyl group ”, the cyano group and the above“ tri ” The same or different 1 to 5 substituents selected from the group consisting of (C ₁ -C ₆ alkyl) silicon group are optionally substituted phenylsulfonyl groups, such as phenylsulfonyl, fluorophenylsulfonyl, Difluorophenylsulfonyl, trifluorophenylsulfonyl, chlorophenylsulfonyl, dichlorophenylsulfonyl, trichlorophenylsulfonyl, fluorochloro Phenylsulfonyl, methylphenylsulfonyl, dimethylphenylsulfonyl, trimethylphenylsulfonyl, tetramethylphenylsulfonyl, pentamethylphenylsulfonyl, ethylphenylsulfonyl, fluoro (methyl) phenylsulfonyl, chloro (methyl) phenylsulfonyl, bromo (methyl) phenylsulfonyl, Can be cyclopropylphenylsulfonyl, cyclopropyl (fluoro) phenylsulfonyl, chloro (cyclopropyl) phenylsulfonyl, cyclopropyl (methyl) phenylsulfonyl, (trifluoromethyl) phenylsulfonyl or fluoro (trifluoromethyl) phenylsulfonyl groups; preferably, fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, a chlorine atom and smell C ₁ -C ₃ alkyl group "1-3 substituents selected same or different from the group consisting of atom-substituted, C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ Alkyl) a phenylsulfonyl group which may be substituted with 1 to 3 identical or different substituents selected from the group consisting of silicon groups, and more preferably phenylsulfonyl, chlorophenylsulfonyl, methylphenylsulfonyl, tri A fluorophenylsulfonyl or cyanophenylsulfonyl group;

In the compound (I) and the like used in the production method of the present invention, the “di (C ₁ -C ₆ alkyl) sulfamoyl group” such as the substituent group E is the same or different two “C ₁ -C `` ₆ alkyl group '' is a sulfamoyl group bonded to a nitrogen atom, and can be, for example, dimethylsulfamoyl, methylethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl or dihexylsulfamoyl , Preferably a sulfamoyl group in which two identical or different C ₁ -C ₃ alkyl groups are bonded, more preferably a dimethylsulfamoyl group or a diethylsulfamoyl group, and even more preferably , A dimethylsulfamoyl group.

In the preparation the compounds used in the method (I) or the like of the present invention, "optionally substituted 3- to 6-membered Hajime Tamaki optionally such R ³ (the heterocycle, in the ring, one nitrogen atom , An oxygen atom or a sulfur atom, may further contain 1 to 2 nitrogen atoms, may be condensed with a benzene ring, and the substituent is a substituent selected from substituent group E Is the same or different 1 to 3 substituents selected from the group consisting of the “halogen atom”, the “C ₁ -C ₆ alkyl group” and the “C ₁ -C ₆ haloalkyl group”. A group or a hydroxyl group, the above-mentioned “optionally substituted phenylsulfonyl group (the substituent is a substituent selected from substituent group A)” or the “di (C ₁ -C ₆ alkyl) sulfamoyl”. May be substituted by "group" and condensed with benzene ring “As a heteroatom, a 3-, 6-membered heterocyclic group which contains one nitrogen atom, oxygen atom or sulfur atom, and may further contain 1-2 nitrogen atoms” And preferably, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group and “1-3 identical or different substituents selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom” ₁ or 2 substituents selected from the group consisting of “substituted C ₁ -C ₃ alkyl group”, or a hydroxyl group, “fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group” , (C ₁ -C ₃ alkyl group substituted by 1 to 3 identical or different substituents selected from the group consisting of fluorine atom, chlorine atom and bromine atom), C ₃ -C ₄ cycloalkyl group, cyano From the group consisting of groups and tri (C ₁ -C ₃ alkyl) silicon groups The same or different selected 1 to 3 substituents optionally substituted phenylsulfonyl group "or" the same or different 2 C ₁ -C ₃ alkyl group bonded sulfamoyl group "is substituted. And may be condensed with a benzene ring, “as a hetero atom, containing one nitrogen atom, oxygen atom or sulfur atom, and further containing one nitrogen atom, 3 ˜6-membered heterocyclic group ”, more preferably the same 1-2 substituents selected from the group consisting of chlorine atom, bromine atom, methyl group, ethyl group and trifluoromethyl group, or hydroxyl group , Phenylsulfonyl group, tolylsulfonyl group or dimethylsulfamoyl group may be substituted, aziridine, oxiranyl, oxetanyl, pyrrolyl, furyl, thienyl, pyrazolyl, thiazolyl Pyridyl, benzimidazolyl or benzothiazolyl, and even more preferably, thienyl, pyrazolyl or It is a thiazolyl group.

In the compound (I) and the like used in the production method of the present invention, “(C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group” such as R ³ is bonded to an alkoxy group having 1 to 6 carbon atoms. Alkoxy groups having 1 to 6 carbon atoms, for example, methoxymethoxy, ethoxymethoxy, propoxymethoxy, butoxymethoxy, s-butoxymethoxy, t-butoxymethoxy, pentyloxymethoxy, hexyloxymethoxy, methoxyethoxy, ethoxyethoxy , Propoxyethoxy, butoxyethoxy, methoxypropoxy, methoxybutoxy, methoxypentyloxy or methoxyhexyloxy group, preferably an alkoxy group having 1 to 3 carbon atoms substituted by an alkoxy group having 1 to 3 carbon atoms More preferably, methoxyethoxy, ethoxyeth A sheet or ethoxymethoxy group.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted phenoxy group such as R ³ (the substituent is substituted with a hydroxyl group or a halogen atom and a C ₁ -C ₆ alkoxy group”). Is a phenoxy group optionally substituted by one hydroxyl group, or the group consisting of the “halogen atom” and the “C ₁ -C ₆ alkoxy group”. A phenoxy group substituted by a pyridazinyloxy group substituted with 1 to 3 identical or different substituents selected from: preferably a hydroxyphenoxy group, or a fluorine atom, a chlorine atom, a bromine atom and a C ₁ -C ₃ phenoxy groups pyridazinyloxy group the same or different 1 to 2 substituents is substituted selected from the group consisting of an alkoxy group is substituted, more preferably, EnsoHara And, pyridazinyloxy group methoxy or ethoxy group substituted by 1 is a phenoxy group substituted.

In the preparation the compounds used in the method (I) or the like of the present invention, "substituted optionally 5-6 membered heterocyclic group (said heterocyclic may be such as R ³ is, in the ring, the one, nitrogen An atom, an oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms, and the substituent is a substituent selected from the substituent group E). atom ", the" C ₁ -C ₆ alkyl group ", the" C ₁ -C ₆ haloalkyl group ", a hydroxyl group, the" optionally substituted phenylsulfonyl group (the substituent is selected from the substituent group A And the above-mentioned “di (C ₁ -C ₆ alkyl) sulfamoyl group” may be substituted with the same or different one or two substituents selected from the group consisting of the above-mentioned “ A 5- to 6-membered heterocyclic group (the heterocyclic ring contains one nitrogen atom in the ring; A group (5 to 6-membered heterocyclic oxy group) in which an oxygen atom is bonded to an atom, an oxygen atom, or a sulfur atom, and may further contain 1 to 2 nitrogen atoms. the fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, one to three substituents the same or different selected from the group consisting of chlorine atom and bromine atom is substituted C ₁ -C ₃ alkyl group ”, hydroxyl group,“ fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, (the same or different 1 selected from the group consisting of fluorine atom, chlorine atom and bromine atom ” to three C ₁ substituent is substituted -C ₃ alkyl group), C ₃ -C ₄ cycloalkyl group, the same or different selected from cyano group and the group consisting of tri (C ₁ -C ₃ alkyl) silyl group 1 to 3 substituents optionally substituted by phenyls The same or different 1 or 2 substituents selected from the group consisting of “a sulfonyl group” and “a sulfamoyl group to which two identical or different C _{1 to} C ₃ alkyl groups are bonded” may be substituted; “5-6 membered heterocyclic oxy group which contains one nitrogen atom, oxygen atom or sulfur atom as a heteroatom, and may further contain one nitrogen atom”, more preferably Are one or two different substituents selected from the group consisting of chlorine atom, bromine atom, methyl group, ethyl group, trifluoromethyl group, hydroxyl group, phenylsulfonyl group, tolylsulfonyl group and dimethylsulfamoyl group. Optionally substituted pyridyloxy, pyrrolyloxy, furyloxy, thienyloxy, pyrazolyloxy, thiazolyloxy, pyrimidyloxy, pyrazinyloxy or pyrida A Niruokishi group, still more preferably a good pyridazinyloxy group chlorine atom and a hydroxyl group is also substituted.

In the compound or the like used in the production method of the present invention, “optionally substituted benzoyloxy group (the substituent is a substituent selected from Substituent Group A)” such as R ³ is the above-mentioned. A group (benzoyloxy group) in which an oxygen atom is bonded to a “benzoyl group (the substituent is a substituent selected from substituent group A)”, for example, benzoyloxy, fluorobenzoyloxy, difluorobenzoyloxy , Trifluorobenzoyloxy, chlorobenzoyloxy, dichlorobenzoyloxy, trichlorobenzoyloxy, fluorochlorobenzoyloxy, methylbenzoyloxy, dimethylbenzoyloxy, trimethylbenzoyloxy, tetramethylbenzoyloxy, pentamethylbenzoyloxy, ethylbenzoyloxy Fluoro (methyl) benzoyloxy, chloro (methyl) benzoyloxy, bromo (methyl) benzoyloxy, cyclopropylbenzoyloxy, cyclopropyl (fluoro) benzoyloxy, chloro (cyclopropyl) benzoyloxy, cyclopropyl (methyl) benzoyloxy, It is a (trifluoromethyl) benzoyloxy, fluoro (trifluoromethyl) benzoyloxy or cyanobenzoyl group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, chlorine atom and 1-3 substituents C ₁ -C ₃ alkyl group substituted with selected same or different from the group consisting of a bromine atom ", C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C selected from ₁ -C ₃ alkyl) group consisting of silicon group The same or different 1 to 3 substituents may be substituted benzoyloxy groups, and more preferably benzoyloxy, chlorobenzoyloxy, dichlorobenzoyloxy, methylbenzoyloxy, trifluorobenzoyloxy or cyano Benzoyloxy group.

In the compound (I) and the like used in the production method of the present invention, “optionally substituted phenylsulfonyloxy group such as R ³ (the substituent is a substituent selected from substituent group A)”. ”Means the“ halogen atom ”, the“ C ₁ -C ₆ alkyl group ”, the“ C ₁ -C ₆ haloalkyl group ”, the“ C ₃ -C ₆ cycloalkyl group ”, the cyano group and the“ tri ( ₁ to 5 substituents selected from the group consisting of “C ₁ -C ₆ alkyl) silicon group” are optionally substituted phenylsulfonyloxy groups, such as phenylsulfonyloxy, fluorophenylsulfonyl Oxy, difluorophenylsulfonyloxy, trifluorophenylsulfonyloxy, chlorophenylsulfonyloxy, dichlorophenylsulfonyloxy, tri Chlorophenylsulfonyloxy, fluorochlorophenylsulfonyloxy, methylphenylsulfonyloxy, dimethylphenylsulfonyloxy, trimethylphenylsulfonyloxy, tetramethylphenylsulfonyloxy, pentamethylphenylsulfonyloxy, ethylphenylsulfonyloxy, fluoro (methyl) phenylsulfonyloxy, chloro (Methyl) phenylsulfonyloxy, bromo (methyl) phenylsulfonyloxy, cyclopropylphenylsulfonyloxy, cyclopropyl (fluoro) phenylsulfonyloxy, chloro (cyclopropyl) phenylsulfonyloxy, cyclopropyl (methyl) phenylsulfonyloxy, (tri Fluoromethyl) phenylsulfonyloxy or fluoro (tri Ruoromechiru) be a phenylsulfonyloxy group, preferably a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, "a fluorine atom, the same or different selected from the group consisting of chlorine and bromine identical to 1 to 3 substituents are selected from the group consisting of C ₁ -C ₃ alkyl group ", C ₃ -C ₄ cycloalkyl group, a cyano group and a tri (C ₁ -C ₃ alkyl) silyl group substituted with Or a phenylsulfonyloxy group which may be substituted by 1 to 3 different substituents, more preferably phenylsulfonyloxy, chlorophenylsulfonyloxy, methylphenylsulfonyloxy, trifluorophenylsulfonyloxy or cyanophenyl A sulfonyloxy group.

In the compound (I) and the like used in the production method of the present invention, the “hydroxy C ₁ -C ₆ alkyl group” such as R ³ is a C ₁ -C ₆ alkyl group substituted with ₁ to 2 hydroxyl groups. For example, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1,2-dihydroxypropyl, 1,3-dihydroxy Propyl, 2,3-dihydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 1-hydroxy -1-methylpropyl, 1- (hydroxymethyl) propyl, 2-hydroxy-1-methyl Propyl, 3-hydroxy-1-methylpropyl, 1- (hydroxymethyl) -2-methylpropyl, 2-hydroxy-1,2-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 2-hydroxy-1 , 1-dimethylethyl, 1-hydroxypentyl, 5-hydroxypentyl, 2-hydroxyhexyl or 6-hydroxyhexyl group, preferably hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy Propyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, more preferably hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl It is 3-hydroxypropyl, and even more preferably a 3-hydroxypropyl.

R ³ such as compound (I) used in the production method of the present invention, such as R ³ , which is formed by combining two adjacent carbon atoms with each other, and optionally substituted 3 to 6 members A cyclic hydrocarbon group (the cyclic hydrocarbon may be interrupted by the same or different 1 or 2 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom; atom, a C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy, oxo, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group, C ₁ -C ₆ When the alkyl group is substituted, it may be combined with another C ₁ -C ₆ alkyl group or a carbon atom on the ring to form a new three-membered ring. "C ₁ -C ₆ alkyl group", the "hydroxy The same or different ₁ to ₆ selected from the group consisting of “C ₁ -C ₆ alkyl group”, the “C ₁ -C ₆ alkoxy group”, the oxo group, the hydroxyimino group and the “C ₁ -C ₆ alkoxy imino group”. 4 substituents may be substituted and may be interrupted by the same or different 1 or 2 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur atoms, saturated or unsaturated A 3- to 6-membered cyclic hydrocarbon group, which may further form a cyclopropane ring on the ring, and preferably two adjacent groups such as R ³ are joined together to form the formula —CH ₂ —. _{, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 -, - C (CH 3) 2 CH 2 _{CH 2 -, - CH 2 C} (CH 3) 2 CH 2 -, - CH (OCH 3) CH 2 CH 2 _{, -C (OCH 3) 2 CH} 2 CH 2 -, - CH 2 C (OCH 3) 2 CH 2 -, - C (= O) CH 2 CH 2 -, - CH 2 C (= O) CH 2 - _{, -C (= NOCH 3) CH} 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 CH 2 CH 2 -, - C (CH 3) 2 CH 2 CH 2 CH ₂ —, —CH (OCH ₃ ) CH ₂ CH ₂ CH ₂ —, —CH═CH—CH═CH—, —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, —OCH ₂ CH ( _{CH 3) -, - OC (} CH 3) 2 CH 2 -, - OCH = CH -, - OC (CH 3) = CH -, - OCH = C (CH 3) -, - SCH = CH -, - N = CH-CH = CH -, - OCH 2 O -, - OCH (CH 3) O -, - OC (CH 3) 2 O -, - OCF 2 O -, - OCH 2 CH 2 O -, - OCH = _{N -, - OC (CH 3} ) = N-,

で表される基を形成し、より好適には、Ｒ³等の隣合う２個が、一緒になって、式−ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ＝ＣＨ−ＣＨ＝ＣＨ−、−ＯＣＨ₂ＣＨ₂−、−ＯＣＨ＝ＣＨ−、−ＯＣＨ＝Ｃ（ＣＨ₃）−、−ＳＣＨ＝ＣＨ−、−Ｎ＝ＣＨ−ＣＨ＝ＣＨ−、−ＯＣＨ₂Ｏ−、−ＯＣＨ₂ＣＨ₂Ｏ−、

More preferably, two adjacent groups such as R ³ are joined together to form the formula —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH _{3) CH 2 CH 2 -,} - CH 2 CH 2 CH 2 CH 2 -, - CH = CH-CH = CH -, - OCH 2 CH 2 -, - OCH = CH -, - OCH = C (CH 3) -, - SCH = CH -, - N = CH-CH = CH -, - OCH 2 O -, - OCH 2 CH 2 O-,

で表される基を形成し、更により好適には、Ｒ³等の隣合う２個が、一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₂−、−ＯＣＨ₂ＣＨ₂−、−ＯＣＨ＝ＣＨ−又は

And more preferably, two adjacent groups such as R ³ are taken together to form the formula —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH _{2. -, - OCH 2 CH 2 -} , - OCH = CH- or

で表される基を形成する。

Is formed.

で表される基を形成し、
より好適には、（３ｂ）互いに独立して、水素原子、ハロゲン原子、置換されていてもよいＣ₁〜Ｃ₄アルキル基（当該置換基は、１〜３個のフッ素原子、又は、１個のシクロプロピル基である。）、置換されてよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、フッ素原子、塩素原子、臭素原子、Ｃ₁〜Ｃ₂アルキル基、シクロプロピル基及びＣ₁〜Ｃ₂アルコキシ基からなる群から選ばれる同一の１〜２個の置換基である。）、ニトロ基、Ｃ₁〜Ｃ₃アルコキシ基又はトリフルオロメトキシ基であるか、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷のうち、隣合う２個が一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₂−、−ＯＣＨ₂ＣＨ₂−、−ＯＣＨ＝ＣＨ−又は

で表される基を形成し、但し、Ｒ³は水素原子ではなく、
さらにより好適には、（３ｃ）互いに独立して、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₃アルキル基、置換されてよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、塩素原子及びＣ₁〜Ｃ₂アルキル基からなる群から選ばれる同一の１〜２個の置換基である。）又はＣ₁〜Ｃ₂アルコキシ基であるか、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷のうち、隣合う２個が一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂−又は−ＯＣＨ＝ＣＨ−で表される基を形成し、但し、Ｒ³は水素原子ではなく、
特に好適には、（３ｄ）水素原子、ハロゲン原子、メチル基、エチル基、イソプロピル基、置換されてよいシクロプロピル基（当該置換基は、２個の塩素原子である。）又はメトキシ基であり、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷のうち、隣合う２個が一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂−で表される基を形成し、但し、Ｒ³は水素原子ではなく、
最も好適には、（３ｅ）Ｒ³が、塩素原子、臭素原子、メチル基、エチル基、イソプロピル基又はシクロプロピル基であり、Ｒ⁴が、水素原子又はメチル基であるか、又はＲ³とＲ⁴が、一緒になって、式 式−ＣＨ₂ＣＨ₂ＣＨ₂−で表される基を形成し、
Ｒ⁵が、水素原子であり、Ｒ⁶が、水素原子又はメチル基であり、Ｒ⁷が水素原子、塩素原子又はメチル基である。 In addition, in the compound (I) used in the production method of the present invention,
R ¹ is
Preferably, (1a) a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is 1 to 3 fluorine atoms. ), A cyclopropyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, an optionally substituted phenyl group {the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C _{1 to} C ₃ haloalkyl group (the halogen atom is the same or different 1 to 3 halogen atoms selected from the group consisting of fluorine atom, chlorine atom and bromine atom), cyclopropyl group and tri (C _{1 to} C ₃ alkyl) are the same or different one or two substituents selected from the group consisting of silicon groups. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy groups, optionally substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ ~ C ₃ haloalkyl group (said halogen atom is 1 to 3 fluorine atoms.), the same or different 1 to 2 selected from the group consisting of cyclopropyl group, and tri (C ₁ -C ₃ alkyl) silyl group Substituents. } Or substituted pyrazolyloxy group (the substituent is two one benzoyl group and two C ₁ -C ₃ alkyl group substituted by a chlorine atom.), And
More preferably, (1b) is a chlorine atom, a bromine atom or a trifluoromethyl group,
Even more preferably, (1c) is a chlorine atom or a bromine atom,
Particularly preferred is (1d) a chlorine atom,
R ² is
Preferably, (2a) a hydrogen atom, a halogen atom, C ₁ -C ₃ alkyl group, (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, an optionally substituted benzoyl group {said substituent , Fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (the halogen atom is the same or different selected from the group consisting of fluorine atom, chlorine atom and bromine atom) 1 to 3 halogen atoms), ₁ to 2 identical or different substituents selected from the group consisting of a cyclopropyl group and a tri (C ₁ -C ₃ alkyl) silicon group. }, Substituted optionally may phenoxy group {said substituent be a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is fluorine atom, chlorine The same or different 1 to 3 halogen atoms selected from the group consisting of atoms and bromine atoms), the same or different selected from the group consisting of cyclopropyl groups and tri (C ₁ -C ₃ alkyl) silicon groups 1 to 2 different substituents. }, The same or different 1 or 2 substituents selected from the group consisting of a cyclopropyl group and a tri (C ₁ -C ₃ alkyl) silicon group. } Or a tri (C ₁ -C ₃ alkyl) silicon group,
More preferably, (2b) is a hydrogen atom, a halogen atom, a methyl group or a trimethylsilyl group,
Even more preferably, (2c) is a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are
Preferably, independently of one another (3a), a hydrogen atom, a halogen atom, a substituted C ₁ optionally -C ₄ alkyl group (the substituent is selected from fluorine atom, the group consisting of chlorine and bromine Or the same or different 1 to 3 substituents or a C _{3 to} C ₄ cycloalkyl group), an optionally substituted C _{3 to} C ₅ cycloalkyl group (the substituent is a fluorine atom) is chlorine atom, bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ same or different 1 to 3 substituents selected from the group consisting of cycloalkyl group and C ₁ -C ₃ alkoxy groups ), C ₆ -C ₇ bicycloalkyl group, optionally substituted phenyl group {the substituent is a fluorine atom, chlorine atom, bromine atom, C ₁ -C ₃ alkyl group or C ₁ -C ₃ haloalkyl group (The halogen atom is a fluorine atom, salt Is an atom and 1 to 3 halogen atoms which selected same or different from the group consisting of bromine atoms.) It is. }, An optionally substituted 5- to 6-membered heterocyclic group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms may contain, the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and a bromine atom The same or different 1 to 3 halogen atoms selected from the group consisting of: 1 to 2 identical or different substituents selected from the group consisting of: }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), or an optionally substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinyloxy substituted by any of a bromine atom and C ₁ -C ₃ alkoxy groups Or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are combined together to form the formula —CH ₂ CH ₂ —, —CH ₂ CH. ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH═CH—CH═CH—, —OCH ₂ CH ₂ —, —OCH═CH— _{, -OCH = C (CH 3)} -, - SCH = CH -, - N = CH-CH = CH _{-, - OCH 2 O -,} - OCH 2 CH 2 O-,

A group represented by
More preferably, (3b) independently of one another, a hydrogen atom, a halogen atom, an optionally substituted C ₁ -C ₄ alkyl group (the substituent is one to three fluorine atoms, or, one A C ₃ -C ₄ cycloalkyl group which may be substituted (the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₂ alkyl group, a cyclopropyl group and a C _1). -C is a ₂ identical one to two substituents selected from the group consisting of an alkoxy group.), a nitro group, or a C ₁ -C ₃ alkoxy group or a trifluoromethoxy group, or, R ^3, R ⁴ , R ⁵ , R ⁶ and R ⁷ , two adjacent ones are taken together to form the formula —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH ₂ —, —OCH ₂ CH _2. -, -OCH = CH- or

In which R ³ is not a hydrogen atom,
Even more preferably, (3c) independently of one another are hydrogen atom, halogen atom, C ₁ -C ₃ alkyl group may be substituted C ₃ -C ₄ cycloalkyl group (said substituent is a chlorine atom and a C ₁ to ₂ identical substituents selected from the group consisting of _{1 to} C ₂ alkyl groups) or C _{1 to} C ₂ alkoxy groups, or R ³ , R ⁴ , R ⁵ , R ^6. And R ⁷ , two adjacent groups together form a group represented by the formula —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, provided that R ³ is not a hydrogen atom,
Particularly preferred is (3d) a hydrogen atom, a halogen atom, a methyl group, an ethyl group, an isopropyl group, an optionally substituted cyclopropyl group (the substituent is two chlorine atoms) or a methoxy group. Or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are joined together to form a group represented by the formula —CH ₂ CH ₂ CH ₂ —, R ³ is not a hydrogen atom,
Most preferably, (3e) R ³ is a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group or a cyclopropyl group, and R ⁴ is a hydrogen atom or a methyl group, or R ³ and R ⁴ together form a group of the formula —CH ₂ CH ₂ CH ₂ —
R ⁵ is a hydrogen atom, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom, a chlorine atom or a methyl group.

で表される基を形成する化合物、
（Ｂ）Ｒ¹が、塩素原子、臭素原子又はトリフルオロメチル基であり、
Ｒ²が、水素原子、ハロゲン原子、メチル基又はトリメチルシリル基であり、
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、互いに独立して、水素原子、ハロゲン原子、置換されていてもよいＣ₁〜Ｃ₄アルキル基（当該置換基は、１〜３個のフッ素原子、又は、１個のシクロプロピル基である。）、置換されていてもよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、フッ素原子、塩素原子、臭素原子、Ｃ₁〜Ｃ₂アルキル基、シクロプロピル基及びＣ₁〜Ｃ₂アルコキシ基からなる群から選ばれる同一の１〜２個の置換基である。）、ニトロ基、Ｃ₁〜Ｃ₃アルコキシ基又はトリフルオロメトキシ基であるか、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷のうち、隣合う２個が一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ（ＣＨ₃）ＣＨ₂ＣＨ₂−、−ＯＣＨ₂ＣＨ₂−、−ＯＣＨ＝ＣＨ−又は

で表される基を形成し、Ｒ³は水素原子ではない化合物、
（Ｃ）Ｒ¹が、塩素原子又は臭素原子であり、
Ｒ²が、水素原子であり、
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、互いに独立して、水素原子、ハロゲン原子、Ｃ₁〜Ｃ₃アルキル基、置換されていてもよいＣ₃〜Ｃ₄シクロアルキル基（当該置換基は、塩素原子及びＣ₁〜Ｃ₂アルキル基からなる群から選ばれる同一の１〜２個の置換基である。）又はＣ₁〜Ｃ₂アルコキシ基であるか、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷のうち、隣合う２個が、一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂−又は−ＯＣＨ＝ＣＨ− で表される基を形成し、但し、Ｒ³は水素原子ではない化合物、
（Ｄ）Ｒ¹が、塩素原子であり、
Ｒ²が、水素原子であり、
Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷が、互いに独立して、水素原子、ハロゲン原子、メチル基、エチル基、イソプロピル基、置換されていてもよいシクロプロピル基（当該置換基は、２個の塩素原子である。）又はメトキシ基であるか、又は、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷のうち、隣合う２個が、一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂−で表される基を形成し、但し、Ｒ³は水素原子ではない化合物、又は
（Ｅ）Ｒ¹が、塩素原子であり、
Ｒ²が、水素原子であり、
Ｒ³が、塩素原子、臭素原子、メチル基、エチル基、イソプロピル基又はシクロプロピル基であり、Ｒ⁴が、水素原子又はメチル基であるか、又はＲ³とＲ⁴が、一緒になって、式−ＣＨ₂ＣＨ₂ＣＨ₂− で表される基を形成し、Ｒ⁵が、水素原子であり、Ｒ⁶が、水素原子又はメチル基であり、Ｒ⁷が、水素原子、塩素原子又はメチル基である化合物である。
さらにまた、好適な化合物（Ｉ）を、以下に、具体的に例示することができる。
化合物番号１：６−クロロ−３−（２−ヨードフェノキシ）−４−ピリダジノール、
化合物番号２：６−クロロ−３−（２−メチルフェノキシ）−４−ピリダジノール、
化合物番号３：６−クロロ−３−（２−イソプロピルフェノキシ）−４−ピリダジノール、
化合物番号４：６−クロロ−３−（２−シクロプロピルフェノキシ）−４−ピリダジノール、
化合物番号５：６−クロロ−３−［２−（２，２−ジクロロシクロプロピル）フェノキシ］−４−ピリダジノール、
化合物番号６：６−クロロ−３−（２，３−ジヒドロ−１Ｈ−インデン−４−イルオキシ）−４−ピリダジノール、
化合物番号７：３−（１−ベンゾフラン−７−イルオキシ）−６−クロロ−４−ピリダジノール、
化合物番号８：６−クロロ−３−（２，５−ジメチルフェノキシ）−４−ピリダジノール、
化合物番号９：６−クロロ−３−（２−シクロプロピル−５−メチルフェノキシ）−４−ピリダジノール、
化合物番号１０：６−クロロ−３−（２−メトキシ−５−メチルフェノキシ）−４−ピリダジノール、
化合物番号１１：６−クロロ−３−（２−フルオロ−６−イソプロピルフェノキシ）−４−ピリダジノール、
化合物番号１２：６−クロロ−３−（２−クロロ−６−メチルフェノキシ）−４−ピリダジノール、
化合物番号１３：６−クロロ−３−（２−クロロ−６−シクロプロピルフェノキシ）−４−ピリダジノール、
化合物番号１４：３−（２−ブロモ−６−メチルフェノキシ）−６−クロロ−４−ピリダジノール、
化合物番号１５：６−クロロ−３−（２，６−ジメチルフェノキシ）−４−ピリダジノール、
化合物番号１６：６−クロロ−３−（２−エチル−６−メチルフェノキシ）−４−ピリダジノール、
化合物番号１７：６−クロロ−３−（２−シクロプロピル−６−メチルフェノキシ）−４−ピリダジノール、
化合物番号１８：６−クロロ−３−［２−（２，２−ジクロロシクロプロピル）− ６−メチルフェノキシ］−４−ピリダジノール、
化合物番号１９：３−（２−アリル−６−メチルフェノキシ）−６−クロロ−４−ピリダジノール、
化合物番号２０：６−クロロ−３−（２−シクロプロピル−３，５−ジメチルフェノキシ）−４−ピリダジノール、
化合物番号２１：６−クロロ−３−［（５−メチル−２，３−ジヒドロ−１Ｈ−インデン−４−イル）オキシ］−４−ピリダジノール、
化合物番号２２：６−クロロ−３−（６−シクロプロピル−３−フルオロ−２−メチルフェノキシ）−４−ピリダジノール、
化合物番号２３：６−クロロ−３−（６−シクロプロピル−２，３−ジメチルフェノキシ）−４−ピリダジノール、又は
化合物番号２４：６−クロロ−３−（２，３，５，６−テトラメチルフェノキシ）−４−ピリダジノール。
上記化合物において、より好適には、
化合物番号１、２、３、４、６、７、８、１０、１２、１３、１４、１６、１７、１９、２０、２１又は２４の化合物である。
次に、本発明の３−フェノキシ−４−ピリダジノール誘導体（Ｉ）の製造方法を、反応フローを示して、詳述する。
（反応フロー）

上式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＱは、前記と同意義を表す。 Further, R ¹ is selected from (1a) to (1d), R ² is selected from (2a) to (2c), R ³ -R ⁷ is selected from (3a) to (3e), and they are combined. Compounds obtained by
(A) R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to 3 fluorine atoms). ), A cyclopropyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, an optionally substituted phenyl group {the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C _{1 to} C ₃ haloalkyl group (the halogen atom is the same or different 1 to 3 halogen atoms selected from the group consisting of fluorine atom, chlorine atom and bromine atom), cyclopropyl group and tri (C _{1 to} C ₃ alkyl) are the same or different one or two substituents selected from the group consisting of silicon groups. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy groups, optionally substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ ~ C ₃ haloalkyl group (said halogen atom is 1 to 3 fluorine atoms.), the same or different 1 to 2 selected from the group consisting of cyclopropyl group, and tri (C ₁ -C ₃ alkyl) silyl group Substituents. } Or substituted pyrazolyloxy group (the substituent is two one benzoyl group and two C ₁ -C ₃ alkyl group substituted by a chlorine atom.), And
R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group, a (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, an optionally substituted benzoyl group {the substituent is a fluorine atom , a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, the same or different 1 to 3 selected from the group consisting of chlorine and bromine ₁ or 2 substituents selected from the group consisting of a cyclopropyl group and a tri (C ₁ -C ₃ alkyl) silicon group. }, Substituted optionally may phenoxy group {said substituent be a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is fluorine atom, chlorine The same or different 1 to 3 halogen atoms selected from the group consisting of atoms and bromine atoms), the same or different selected from the group consisting of cyclopropyl groups and tri (C ₁ -C ₃ alkyl) silicon groups 1 to 2 different substituents. }, The same or different 1 or 2 substituents selected from the group consisting of a cyclopropyl group and a tri (C ₁ -C ₃ alkyl) silicon group. } Or a tri (C ₁ -C ₃ alkyl) silicon group,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an optionally substituted C ₁ -C ₄ alkyl group (the substituent is a fluorine atom, chlorine The same or different 1 to 3 substituents selected from the group consisting of an atom and a bromine atom, or a C _{3 to} C ₄ cycloalkyl group.), An optionally substituted C _{3 to} C ₅ cycloalkyl group (said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ has the same or different selected from the group consisting of cycloalkyl group and C ₁ -C ₃ alkoxy groups 1 to 3 substituents), a C _{6 to} C ₇ bicycloalkyl group, an optionally substituted phenyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C _{1 to} C ₃ alkyl group). groups or C ₁ -C ₃ haloalkyl group (said halogen atom, The same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom. }, An optionally substituted 5- to 6-membered heterocyclic group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms may contain, the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and a bromine atom The same or different 1 to 3 halogen atoms selected from the group consisting of: 1 to 2 identical or different substituents selected from the group consisting of: }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), or an optionally substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinyloxy substituted by any of a bromine atom and C ₁ -C ₃ alkoxy groups Or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a group of the formula: —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH═CH—CH═CH—, —OCH ₂ CH ₂ —, —OCH = CH -, - OCH = C ( CH 3) -, - SCH = CH -, - N = CH-CH = _{CH -, - OCH 2 O -} , - OCH 2 CH 2 O-,

A compound that forms a group represented by:
(B) R ¹ is a chlorine atom, a bromine atom or a trifluoromethyl group,
R ² is a hydrogen atom, a halogen atom, a methyl group or a trimethylsilyl group,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, or an optionally substituted C ₁ -C ₄ alkyl group (the number of the substituent is 1 to 3 Or a C ₃ -C ₄ cycloalkyl group which may be substituted (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C). _The same 1-2 substituents selected from the group consisting of ₂ alkyl groups, cyclopropyl groups and C ₁ -C ₂ alkoxy groups.), Nitro groups, C ₁ -C ₃ alkoxy groups or trifluoromethoxy groups Or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are combined together to form the formula —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH. ₂ CH ₂ —, —OCH ₂ CH ₂ —, —OCH═CH— or

A compound in which R ³ is not a hydrogen atom,
(C) R ¹ is a chlorine atom or a bromine atom,
R ² is a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group, an optionally substituted C ₃ -C ₄ cycloalkyl group ( the substituents are identical one to two substituents selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group.) or a C ₁ -C ₂ alkoxy group, or, R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ together form a group represented by the formula —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, Where R ³ is not a hydrogen atom,
(D) R ¹ is a chlorine atom;
R ² is a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, a methyl group, an ethyl group, an isopropyl group or an optionally substituted cyclopropyl group (the substituent is 2 chlorine atoms) or a methoxy group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form the formula —CH ₂ CH ₂ CH ₂ — is formed, provided that R ³ is not a hydrogen atom, or (E) R ¹ is a chlorine atom,
R ² is a hydrogen atom,
R ³ is a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isopropyl group or a cyclopropyl group, R ⁴ is a hydrogen atom or a methyl group, or R ³ and R ⁴ are taken together And a group represented by the formula —CH ₂ CH ₂ CH ₂ —, R ⁵ is a hydrogen atom, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom, a chlorine atom or It is a compound that is a methyl group.
Furthermore, suitable compound (I) can be specifically exemplified below.
Compound No. 1: 6-chloro-3- (2-iodophenoxy) -4-pyridazinol,
Compound No. 2: 6-chloro-3- (2-methylphenoxy) -4-pyridazinol,
Compound No. 3: 6-chloro-3- (2-isopropylphenoxy) -4-pyridazinol,
Compound No. 4: 6-chloro-3- (2-cyclopropylphenoxy) -4-pyridazinol,
Compound No. 5: 6-chloro-3- [2- (2,2-dichlorocyclopropyl) phenoxy] -4-pyridazinol,
Compound No. 6: 6-chloro-3- (2,3-dihydro-1H-inden-4-yloxy) -4-pyridazinol,
Compound No. 7: 3- (1-benzofuran-7-yloxy) -6-chloro-4-pyridazinol,
Compound No. 8: 6-chloro-3- (2,5-dimethylphenoxy) -4-pyridazinol,
Compound No. 9: 6-chloro-3- (2-cyclopropyl-5-methylphenoxy) -4-pyridazinol,
Compound No. 10: 6-chloro-3- (2-methoxy-5-methylphenoxy) -4-pyridazinol,
Compound No. 11: 6-chloro-3- (2-fluoro-6-isopropylphenoxy) -4-pyridazinol,
Compound No. 12: 6-chloro-3- (2-chloro-6-methylphenoxy) -4-pyridazinol,
Compound No. 13: 6-chloro-3- (2-chloro-6-cyclopropylphenoxy) -4-pyridazinol,
Compound No. 14: 3- (2-bromo-6-methylphenoxy) -6-chloro-4-pyridazinol,
Compound No. 15: 6-chloro-3- (2,6-dimethylphenoxy) -4-pyridazinol,
Compound No. 16: 6-chloro-3- (2-ethyl-6-methylphenoxy) -4-pyridazinol,
Compound No. 17: 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol,
Compound No. 18: 6-chloro-3- [2- (2,2-dichlorocyclopropyl) -6-methylphenoxy] -4-pyridazinol,
Compound No. 19: 3- (2-allyl-6-methylphenoxy) -6-chloro-4-pyridazinol,
Compound No. 20: 6-chloro-3- (2-cyclopropyl-3,5-dimethylphenoxy) -4-pyridazinol,
Compound No. 21: 6-chloro-3-[(5-methyl-2,3-dihydro-1H-inden-4-yl) oxy] -4-pyridazinol,
Compound No. 22: 6-chloro-3- (6-cyclopropyl-3-fluoro-2-methylphenoxy) -4-pyridazinol,
Compound No. 23: 6-chloro-3- (6-cyclopropyl-2,3-dimethylphenoxy) -4-pyridazinol, or Compound No. 24: 6-chloro-3- (2,3,5,6-tetramethyl) Phenoxy) -4-pyridazinol.
In the above compound, more preferably,
Compound Nos. 1, 2, 3, 4, 6, 7, 8, 10, 12, 13, 14, 16, 17, 19, 20, 21 or 24.
Next, the method for producing the 3-phenoxy-4-pyridazinol derivative (I) of the present invention will be described in detail with reference to a reaction flow.
(Reaction flow)

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and Q are as defined above.

(Process 1)
In step 1, 3-phenoxypyridazine derivative (II) is subjected to a reaction with an oxidizing agent in the presence of a solvent to give 3-phenoxypyridazine 1-oxide derivative (III) and 3-phenoxypyridazine 2-oxide derivative (IV ).
The oxidizing agent used is not particularly limited as long as it converts amines to N-oxide. For example, m-chloroperbenzoic acid (mcpba), peracetic acid, pertrifluoroacetic acid, trifluoroacetic anhydride- Hydrogen peroxide, peroxydichloromaleic acid, dichloromaleic anhydride-hydrogen peroxide, peroxymaleic acid, maleic anhydride-hydrogen peroxide, t-butyl hydroperoxide, t-butyl hydroperoxide-vanadium oxyacetyl Peroxide such as acetonate, t-butyl hydroperoxide-molybdenum chloride, hydrogen peroxide; ozone; or oxygen, preferably peroxide, more preferably maleic anhydride-peroxide Hydrogen oxide, dichloromaleic anhydride-hydrogen peroxide, m-chloroperbenzoic acid (mcpba) or trifluoroacetic anhydride - is hydrogen peroxide, even more preferably, maleic anhydride - hydrogen peroxide.
The amount of the oxidizing agent used in the reaction is usually 0.5 to 100 mol, preferably 1 to 5 mol, and more preferably 2.5 to 3. mol with respect to 1 mol of compound (II). 5 mol.
The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butyl alcohol; acetone, methyl isobutyl ketone, etc. Ketones; Nitriles such as acetonitrile; Esters such as ethyl acetate; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic carbonization such as benzene and toluene Hydrogen; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably nitriles or halogenated hydrocarbons More preferably, acetonitrile, Ren, a dichloroethane, or chloroform, and even more preferably is acetonitrile.
The reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, but is usually −90 ° C. to 200 ° C., preferably −10 ° C. to 80 ° C., preferably 0 ° C. to 50 ° C. is there.
The reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, the type of solvent used and the like, but is usually 30 minutes to 72 hours, and preferably 6 hours to 48 hours.

(Process 2)
In step 2, a mixture of 3-phenoxypyridazine 1-oxide derivative (III) and 3-phenoxypyridazine 2-oxide derivative (IV) is added in the presence or absence of a solvent (preferably in the presence of a solvent). A reaction with a halogenating agent to produce a mixture of 4-halogeno-3-phenoxypyridazine derivative (V) and 3-phenoxypyridazine 2-oxide derivative (IV), which is isolated, Or without isolation (in the same reaction system), preferably without isolation (in the same reaction system), in the presence or absence of a solvent (preferably in the presence of a solvent) It is a step of producing a mixture of 4-halogeno-3-phenoxypyridazine derivative (V) and 3-phenoxypyridazine derivative (II) by reaction with an agent.
The halogenating agent used is not particularly limited as long as the pyridazine nucleus is nucleophilically halogenated. For example, phosphorus oxychloride, phosphorus oxybromide, phosphorus oxyiodide, phosphorus pentachloride, phosphorus pentabromide, etc. (Chloromethylene) dimethylammonium chloride (Beersmeier reagent); carbon tetrachloride-tripheninephosphine; thionyl chloride; sulfuryl chloride; sulfonic acid halide compounds such as benzenesulfonyl chloride and paratoluenesulfonyl chloride; or phosgene And phosgene compounds such as diphosgene and triphosgene, preferably phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride, phosphorus pentabromide, (chloromethylene) dimethylammonium chloride (Beersmeier reagent), thionyl chloride, Sulfuryl chloride, benzenesulfur Nirukurorido a para-toluenesulfonyl chloride or phosgene, more preferably a phosphorus oxychloride or oxybromide, particularly preferably a phosphorus oxychloride.
The amount of the halogenating agent to be used is usually 0.5 to 100 mol, preferably 1 mol with respect to 1 mol of compound (III). 1 to 5 mol.
The solvent used in the reaction with the halogenating agent and the reaction with the reducing agent is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, ketones such as acetone and methyl isobutyl ketone Nitriles such as acetonitrile; Esters such as ethyl acetate; Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Aromatic hydrocarbons such as benzene and toluene Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; aliphatic hydrocarbons such as hexane and cyclohexane; or a mixed solvent thereof, Halogenated hydrocarbons, more preferably dichloroethane or It is chloroform.
The reaction temperature in the halogenation varies depending on the raw material compound, reaction reagent, solvent and the like, but is usually −90 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C.
The reaction time in the halogenation mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, the type of the solvent used, etc., but is usually 5 minutes to 72 hours, preferably 30 minutes to 15 hours. is there.
The reducing agent used is not particularly limited as long as it can reduce pyridazine oxides to pyridazines. For example, phosphorus trichloride, phosphorus tribromide, tri (C ₁ -C ₆ ) alkylphosphine, triphosphite triphosphite. Phosphorus compounds such as (C ₁ -C ₆ ) alkyl; transition metals such as zinc, iron and titanium; tin (II) chloride, samarium iodide, indium (III) chloride, ruthenium (III) chloride, nickel chloride (II) ) Transition metal halide compounds; titanium tetrachloride-ammonium chloride, indium-ammonium chloride and other metal compounds-ammonium salts; aluminum chloride-sodium borohydride, lithium chloride-sodium borohydride, zirconium chloride (IV) -hydrogen Metal halide-borohydride compound such as sodium borohydride; or catalytic reduction catalyst (palladium-carbon, platinum oxide, Raney nickel, etc.) and hydrogen, preferably phosphorus trichloride, phosphorus tribromide, zinc, iron, titanium, tin (II) chloride, nickel (II) chloride, aluminum chloride-sodium borohydride, lithium chloride -Sodium borohydride or catalytic reduction catalyst (palladium-carbon, platinum oxide or Raney nickel) and hydrogen, more preferably phosphorus trichloride, phosphorus tribromide, tin (II) chloride, aluminum chloride-borohydride Sodium or a catalytic reduction catalyst (palladium-carbon, platinum oxide or Raney nickel) and hydrogen, particularly preferably phosphorus trichloride or phosphorus tribromide.
The amount of the reducing agent to be used is usually 0.5 to 100 mol, preferably 1 to 5 mol per 1 mol of compound (IV).
The reaction temperature for reduction mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, the solvent used and the like, but is usually −90 ° C. to 200 ° C., and preferably 0 ° C. to 100 ° C.
The reduction reaction time mainly varies depending on the reaction temperature, raw material compounds, reaction reagents, the type of solvent used, etc., but is usually 5 minutes to 24 hours, and preferably 1 hour to 15 hours. .
After completion of each reaction in the above steps 1 and 2 (first and second steps), the target compound in each step is usually used in the next step without isolation.
If necessary, after the completion of each reaction, if insolubles are present, the solution is appropriately filtered, neutralized as appropriate, and the solvent of the reaction mixture is suitably distilled off (preferably under reduced pressure) to obtain water and water. Add the immiscible organic solvent (eg ether, ethyl acetate, etc.), extract, dry and evaporate the solvent (preferably under reduced pressure) to obtain the target compound (mixture) of each step Can be obtained.

(Process 3)
In step 3, a mixture of a 4-halogeno-3-phenoxypyridazine derivative (V) and a 3-phenoxypyridazine derivative (II) is treated with a base in the presence or absence of a solvent (preferably in the presence of a solvent). In the presence of the compound, it is subjected to a hydrolysis reaction to produce a 3-phenoxy-4-pyridazinol derivative (I) and simultaneously recover the 3-phenoxypyridazine derivative (II).
The base to be used is not particularly limited as long as it is used in the hydrolysis reaction, and is usually a base having a pH of 8 or more. Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium, potassium carbonate and cesium carbonate; or alkali metal salts of organic carboxylic acids such as sodium acetate, potassium acetate, sodium formate and potassium formate, preferably alkali metal hydroxides More preferably, sodium hydroxide or potassium hydroxide is used.
The solvent used is not particularly limited as long as it does not inhibit the reaction and dissolves the starting material to some extent. For example, water; alcohols such as methanol, ethanol, t-butyl alcohol; acetone, methyl isobutyl ketone, etc. Ketones such as acetonitrile; esters such as ethyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane; ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane; benzene, toluene, etc. Aromatic hydrocarbons; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; or a mixed solvent thereof, preferably water, alcohols, nitriles , Ethers, sulfoxides or A mixed solvent of these, more preferably a mixed solvent of water and a mixed solvent or water and dimethoxyethane dimethyl sulfoxide.
The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent used, and the like, but is usually −90 ° C. to 200 ° C., and preferably 10 ° C. to 80 ° C.
The reaction time mainly varies depending on the reaction temperature, the raw material compound, the reaction reagent, the type of the solvent used, etc., but is usually 5 minutes to 48 hours, preferably 30 minutes to 8 hours.
After completion of the reaction in this step, if necessary, the solvent of the reaction mixture is distilled off (preferably under reduced pressure), and water and a water-immiscible organic solvent (for example, ether, ethyl acetate, etc.) are added to separate the mixture. Subjected to liquid extraction, the solvent is distilled off (preferably under reduced pressure) from the separated aqueous layer, or the separated aqueous layer is neutralized and water-immiscible organic solvent (for example, , Ether, ethyl acetate, etc.), and the solvent is distilled off (preferably under reduced pressure) to separate and isolate the 3-phenoxy-4-pyridazinol derivative (I) or a salt thereof and simultaneously separate them. From the water-immiscible organic layer, the solvent can be distilled off (preferably under reduced pressure) to recover and isolate the 3-phenoxypyridazine compound (II). Furthermore, if necessary, the compounds (I) and (II) can be further purified by a conventional method such as a recrystallization method, chromatography or the like.

(Process 1-a)
In step 1-a, the 3-phenoxypyridazine derivative (II) recovered in step 3 is used to subject compound (II) to a reaction with an oxidizing agent in the presence of a solvent to give 3-phenoxypyridazine 1 This is a process for producing a mixture of an oxide derivative (III) and 3-phenoxypyridazine 2-oxide derivative (IV).
By subjecting the obtained mixture to the reaction in Step 2 and the reaction in Step 3 again, the 3-phenoxy-4-pyridazinol derivative (I), which is the target compound, is obtained from the compound (II) recovered in Step 3 above. ) Can be manufactured.
Note that after the completion of each reaction step, prior to the subsequent step, functional groups in R ¹ to R ⁷ of the target compound of each step, as long as it is within the scope of the definition of R ¹ to R ^7, according to a conventional method Functional group conversion is possible.
In Step 3, when at least one of R ¹ and R ² is a chlorine atom, depending on the reaction conditions, the chlorine atom of R ¹ or R ² may be substituted with a hydroxy group in the step.
As the starting compound (II) in Step 1, the method described in Patent Document 1 (WO 3/016286) described above is used, or, for example, Helvetica Chimica Acta, 1954, 37, 121- 131; Pharmaceutical Journal, 1956, 76, 12930-1295; The Journal of Organic Chemistry, 1990, 55, 5418-5420; Journal of Heterocyclic Chemistry (Journal of Heterocyclic Chemistry), 1999, Vol. 30, pages 1135-1142, or a method analogous thereto can be used.
EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these.

Example 1
Preparation of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (1) 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 6-chloro Process for producing a mixture of chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 2-oxide (step 1)
A magnetic stirrer bar was placed in a 1 L eggplant flask, and an isobaric dropping funnel was attached. 3-Chloro-6- (2-cyclopropyl-6-methylphenoxy) pyridazine (32.9 g, purity 90.0%, 0.113 mol), maleic anhydride (55.4 g, 0.565 mol) and acetonitrile (113 mL) was added into the flask. The reaction solution was stirred with a stirrer at room temperature for 40 minutes to completely dissolve 3-chloro-6- (2-cyclopropyl-6-methylphenoxy) pyridazine and maleic anhydride. To this solution, 30% aqueous hydrogen peroxide (34.5 mL, 0.339 mol) in a dropping funnel was added over 20 minutes at room temperature. The reaction solution was stirred at room temperature for 22 hours and then cooled to 0 ° C. 2M-aqueous sodium hydroxide solution (565 mL, 1.13 mol) was added over 30 minutes, and the mixture was stirred at 0 ° C. for 20 minutes. Subsequently, sodium sulfite (28.2 g, 0.22 mol) was added, and the mixture was stirred at 0 ° C. for 30 minutes. A small amount of the precipitated solid was filtered, and then the filtrate was concentrated to remove most of acetonitrile. To the obtained residue was added the solid previously collected by filtration, followed by extraction with ethyl acetate (300 mL). The organic layer was washed with water (300 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was dried under reduced pressure (3-5 mmHg) to give the title mixture (33.2 g) as a brown solid. As a result of quantitative determination (external standard method) by HPLC (high performance liquid chromatography), the content of 1-oxide was 63.6% (yield 68%), and the content of 2-oxide was 17. It was 9% (yield 19%).

(2) Method for producing a mixture of 4,6-dichloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine (Step 2)
A magnetic stirrer bar was placed in a 500 mL three-necked round-bottom flask, and a Dimroth condenser and an isobaric dropping funnel were attached. A mixture (33.2 g) of 1-oxide and 2-oxide obtained in (1) above and dichloroethane (42 mL) were added to the flask. The mixture was stirred with a stirrer at 75 ° C. for 20 minutes to give a dark brown solution. Phosphorus oxychloride (8.59 mL, 92.2 mmol) was added to the dropping funnel and added to the solution at 75 ° C. over 15 minutes. After completion of dropping, the solution was stirred at 75 ° C. for 5 hours. The reaction mixture was cooled to room temperature, phosphorus trichloride (3.75 mL, 43.0 mmol) was added, and the mixture was stirred at room temperature for 2 hr, 50 ° C. for 2 hr, and further at 70 ° C. for 4 hr. Again, the reaction solution was cooled to room temperature and then added dropwise over 30 minutes with water (80 mL). After completion of the dropwise addition, the reaction solution was stirred for 30 minutes to quench excess phosphorus oxychloride and phosphorus trichloride. The resulting solution was extracted with dichloroethane (40 mL). The organic layer was separated, washed with 1M hydrochloric acid (60 mL × 2 times), and concentrated under reduced pressure. The obtained residue was dried under reduced pressure (3-5 mmHg) to obtain the title mixture (34.2 g) as a brown solid. When quantitative (external standard method) by HPLC (high performance liquid chromatography) was performed, the content of 4,6-dichloro compound was 59.7% (yield 90%), and the content of 6-chloro compound was Was 16.0% (yield 98%).

(3) Process for producing 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol and recovery of 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine (Step 3) )
A magnetic stirrer bar was placed in a 500 mL 3-neck-round bottom flask, and a Dim funnel and a constant pressure dropping funnel were attached. Mixture of 4,6-dichloro form and 6-chloro form obtained in (2) above (34.2 g, 4,6-dichloro form: 69.1 mmol, 6-chloro form: 21.0 mmol) And dimethyl sulfoxide (144 mL) were added into the flask. The mixture was stirred with a stirrer at 50-53 ° C. for 15 minutes to give a dark brown solution. A 6M aqueous sodium hydroxide solution (32.2 mL, 193 mmol) was poured into the dropping funnel and added over 15 minutes while heating to 50-53 ° C. The reaction solution was stirred for 4 hours while heating at 50-533 ° C. Thereafter, the mixture was concentrated under reduced pressure, and 130 mL of the solvent was distilled off. Ethyl acetate (62 mL) heated to 60 ° C. was added in the same manner as water (165 mL) heated to 60 ° C. to dissolve the residue, which was poured into a separatory funnel and shaken. The aqueous layer was washed with ethyl acetate (60 mL × twice) heated to 60 ° C., concentrated hydrochloric acid (10.2 mL, 122.4 mmol) was added, and the mixture was stirred for 2 hr. The resulting solid was collected by filtration, washed on the filter paper with water (60 mL × 4 times), and then dried under reduced pressure. The obtained solid (16.81 g) was placed in a 200 mL eggplant flask, t-butyl methyl ether (40 mL) was added, and the mixture was stirred at room temperature for 10 hours. The resulting slurry was filtered, and the resulting solid was dried under reduced pressure to give the title compound (15.77 g, purity 91.4%, yield 75%) as a light brown solid.
The ethyl acetate layers were combined and concentrated, and the resulting residue was dried under reduced pressure to obtain a dark brown gum (12.5 g). Toluene (50 mL) was added to this residue to dissolve soluble components, washed with water (50 mL × 2 times), and concentrated under reduced pressure. The resulting gum was dried under reduced pressure to give 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine (8.38 g, purity 59.8%, recovery rate 92%) as a dark brown gum. As recovered.

(4) Reoxidation of recovered 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine (6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 1-oxide and 6 -Reproduction of a mixture of chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine 2-oxide) (step 1-a)
A magnetic stirrer bar was placed in a 200 mL eggplant flask, and an isobaric dropping funnel was attached. 6-Chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine (8.38 g, purity 59.8%, 19.2 mmol) recovered in (3) above, maleic anhydride (9.41 g, 96.0 mmol) and acetonitrile (20 mL) were added into the flask. The reaction solution was stirred with a stirrer at room temperature for 30 minutes to completely dissolve 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) pyridazine and maleic anhydride. To this solution was added 30% aqueous hydrogen peroxide (5.86 mL, 57.6 mmol) at room temperature over 10 minutes. The reaction solution was stirred at room temperature for 24 hours and then cooled to 0 ° C. 2M aqueous sodium hydroxide solution (96 mL, 192 mmol) was added over 15 minutes and stirred at 0 ° C. for 20 minutes. Subsequently, sodium sulfite (4.80 g, 38.1 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes. After returning to room temperature, the reaction mixture was concentrated, most of the acetonitrile was distilled off, and the resulting residue was extracted with ethyl acetate (100 mL). The organic layer was washed with water (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was dried under reduced pressure (3-5 mmHg) to obtain a mixture (7.36 g) containing 1-oxide and 2-oxide as a brown amorphous substance. When quantification (external standard method) by HPLC (high performance liquid chromatography) was performed, the content of 1-oxide was 46.3% (yield 64%), and the content of 2-oxide was It was 13.7% (yield 19%).
This mixture was reacted and worked up in the same manner as in (2) and (3) above to produce 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol. -3- (2-Cyclopropyl-6-methylphenoxy) pyridazine is recovered again.

  The production method of the present invention can produce a high-purity target product (3-phenoxy-4-pyridazinol derivative) with a simple operation and high yield, and further, a starting material (3-phenoxypyridazine derivative) can be produced. Since it can be reused, it is an industrially extremely advantageous production method for stably producing the 3-phenoxy-4-pyridazinol derivative (I) having excellent herbicidal activity at a low cost and in a high yield.

Claims (7)

General formula

[Wherein, R ¹ represents a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₂ -C ₆ alkenyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, di (C ₁ -C ₆ alkyl) carbamoyl group, optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), 5 -6-membered heterocyclic group (the heterocyclic group may contain one nitrogen atom, oxygen atom or sulfur atom in the ring, and may further contain 1-2 nitrogen atoms). C ₁ -C ₆ alkoxy group, an optionally substituted phenoxy group (the substituent is a substituent selected from substituent group a.), or an optionally substituted 5- to 6-membered heterocyclic oxy group {The heterocyclic group contains one nitrogen atom, oxygen atom or sulfur atom in the ring. Further, it may further contain 1 to 2 nitrogen atoms, and the substituent is an optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A). And a substituent selected from the group consisting of C _{1 to} C ₆ alkyl groups. },
R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₆ alkyl group, a (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkyl group, an optionally substituted benzoyl group (the substituent is the following substituent) A substituent selected from group A.), a C ₂ -C ₇ alkoxycarbonyl group, an optionally substituted phenoxy group (the substituent is a substituent selected from the following substituent group A), substitution An optionally substituted phenylthio group (the substituent is a substituent selected from the following substituent group A) or a tri (C ₁ -C ₆ alkyl) silicon group;
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, or an optionally substituted C ₁ -C ₆ alkyl group (the substituent is represented by the following substituent group B) A C ₂ -C ₆ alkenyl group which may be substituted (the substituent is a cyano group or a nitro group), a C ₂ -C ₆ alkynyl group, a substituted group. C ₃ -C ₆ cycloalkyl group (the substituent is a substituent selected from the following substituent group C), C ₄ -C ₁₀ bicycloalkyl group, cyano group, formyl group, C ₂ -C ₇ alkylcarbonyl group, optionally substituted benzoyl group (the substituent is a substituent selected from the following substituent group A), carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, carbamoyl group, di ( C ₁ -C ₆ alkyl) carbamoyl group, location An optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), an optionally substituted 3- to 6-membered heterocyclic group (the heterocyclic ring is in the ring, It contains one nitrogen atom, oxygen atom or sulfur atom, may further contain 1 to 2 nitrogen atoms, may be condensed with a benzene ring, and the substituent is the following substituent group A substituent selected from E.), an optionally substituted amino group (the substituent is a substituent selected from the following substituent group D), a nitro group, a hydroxyl group, C ₁ -C ₆ alkoxy. Group, C ₁ -C ₆ haloalkoxy group, (C ₁ -C ₆ alkoxy) C ₁ -C ₆ alkoxy group, optionally substituted phenoxy group (the substituent is a hydroxyl group or a halogen atom and C ₁ -C pyridazinium substituted by ₆ alkoxy group Gini an oxy group. An optionally substituted 5- to 6-membered heterocyclic oxy group (the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further 1 to 2 nitrogen atoms) The substituent may be contained, and the substituent is a substituent selected from the following substituent group E.), and an optionally substituted benzoyloxy group (the substituent is a substituent selected from the following substituent group A) in a.), optionally substituted phenylsulfonyloxy group (the substituent is a substituent selected from substituent group a.), C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl Represents a group, a C ₁ -C ₆ alkylsulfonyl group or a tri (C ₁ -C ₆ alkyl) silicon group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ that are adjacent to each other. Each substituted with a carbon atom to which it is attached A good 3- to 6-membered cyclic hydrocarbon group (the hydrocarbon group may be interrupted by the same or different 1-2 heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, substituent is halogen atom, C ₁ -C ₆ alkyl group, a hydroxy C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy, oxo, hydroxyimino group or a C ₁ -C ₆ alkoxyimino group, When the C ₁ -C ₆ alkyl group is substituted, it may be bonded to another C ₁ -C ₆ alkyl group or a carbon atom on the ring to form a new 3-membered ring. )
Substituent group A is a group consisting of halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, C ₃ -C ₆ cycloalkyl group, a cyano group and a (C ₁ -C ₆ alkyl) silyl group And
Substituent group B, a halogen atom, C ₃ -C ₆ cycloalkyl group, a cyano group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a phenyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, consisting of C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, C ₁ -C ₄ alkyl dioxy group, hydroxyimino group and C ₁ -C ₆ alkoxyimino group A group,
Substituent group C is a halogen atom, an optionally substituted C ₁ -C ₆ alkyl group (the substituent is a substituent selected from the following substituent group B), C ₃ -C ₆ cycloalkyl group. , C ₂ -C ₆ alkenyl group, cyano group, C ₂ -C ₇ alkylcarbonyl group, a benzoyl group, a carboxyl group, C ₂ -C ₇ alkoxycarbonyl group, a carbamoyl group, a di (C ₁ -C ₆ alkyl group) carbamoyl Group, an optionally substituted phenyl group (the substituent is a substituent selected from the following substituent group A), a 5- to 6-membered heterocyclic group (the heterocyclic ring has one , A nitrogen atom, an oxygen atom or a sulfur atom, and further may contain 1 to 2 nitrogen atoms.), An optionally substituted amino group (the substituent is from the following substitution group D) Selected substituents), nitro groups, hydroxyl groups, ₁ -C ₆ alkoxy groups, C ₁ -C ₆ haloalkoxy group, a phenoxy group, C ₁ -C ₆ alkylthio group, Fenichio group, C ₁ -C ₆ alkylsulfinyl group consisting Le group and C ₁ -C ₆ alkylsulfonyl group And
Substituent group D is, C ₁ -C ₆ alkyl group, C ₂ -C ₇ alkylcarbonyl group, C ₂ -C ₇ alkoxycarbonyl group, a di (C ₁ -C ₆ alkyl group) carbamoyl group and a C ₁ -C ₆ A group consisting of alkylsulfonyl groups,
Substituent group E includes a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a hydroxyl group, and an optionally substituted phenylsulfonyl group (the substituent is a substituent selected from the following substituent group A) Group) and di (C ₁ -C ₆ alkyl) sulfamoyl groups. ]
A process for producing a 3-phenoxy-4-pyridazinol derivative (I) represented by:
General formula

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
A 3-phenoxypyridazine derivative (II) represented by the general formula

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
3-phenoxypyridazine 1-oxide derivative (III) represented by:
General formula

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
To obtain a mixture with 3-phenoxypyridazine 2-oxide derivative (IV) represented by:
Subsequently, this mixture is subjected to a reaction with a halogenating agent,
General formula

(In the formula, Q represents a halogen atom, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined above.)
To obtain a mixture of a 4-halogeno-3-phenoxypyridazine derivative (V) and a 3-phenoxypyridazine 2-oxide derivative (IV) represented by the formula:
Subsequently, this mixture is subjected to a reaction with a reducing agent,
A mixture of 4-halogeno-3-phenoxypyridazine derivative (V) and 3-phenoxypyridazine derivative (II) was obtained,
Subsequently, the mixture is subjected to a hydrolysis reaction under basic conditions.
Thereafter, if necessary, the solvent of the reaction mixture is distilled off, water and a water-immiscible organic solvent are added, liquid separation extraction is performed, and 3-phenoxy-4-pyridazinol derivative (I) is obtained from the aqueous layer. A method for producing a 3-phenoxy-4-pyridazinol derivative (I), comprising separating and simultaneously recovering the 3-phenoxypyridazine derivative (II) from the water-immiscible organic layer.   In addition to the operation of claim 1, the recovered 3-phenoxypyridazine derivative (II) is reacted with an oxidant, a reaction with a halogenating agent, a reaction with a reducing agent and a base in the same manner as in claim 1. The reaction mixture is subjected to a hydrolysis reaction under acidic conditions, followed by liquid separation extraction to separate the 3-phenoxy-4-pyridazinol derivative (I) from the aqueous layer, and at the same time from the water-immiscible organic layer 3 The method according to claim 1, wherein the operation of recovering the phenoxypyridazine derivative (II) is further repeated at least once, and the recovered 3-phenoxypyridazine derivative (II) is reused. In the 3-phenoxy-4-pyridazinol derivative (I),
R ¹ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is 1 to 3 fluorine atoms), cyclo A propyl group, a di (C ₁ -C ₃ alkyl) carbamoyl group, an optionally substituted phenyl group {the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group (the halogen atom is the same or different 1 to 3 halogen atoms selected from the group consisting of fluorine atom, chlorine atom and bromine atom), cyclopropyl group and tri (C ₁ -C 1 or 2 substituents selected from the group consisting of ( ₃ alkyl) silicon groups. }, A furyl group, a thienyl group, C ₁ -C ₃ alkoxy groups, optionally substituted phenoxy group {said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ ~ C ₃ haloalkyl group (said halogen atom is 1 to 3 fluorine atoms.), the same or different 1 to 2 selected from the group consisting of cyclopropyl group, and tri (C ₁ -C ₃ alkyl) silyl group Substituents. } Or substituted pyrazolyloxy group (the substituent is two one benzoyl group and two C ₁ -C ₃ alkyl group substituted by a chlorine atom.), And
R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group, a (C ₁ -C ₃ alkoxy) C ₁ -C ₃ alkyl group, an optionally substituted benzoyl group {the substituent is a fluorine atom , a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, the same or different 1 to 3 selected from the group consisting of chlorine and bromine ₁ or 2 substituents selected from the group consisting of a cyclopropyl group and a tri (C ₁ -C ₃ alkyl) silicon group. }, Substituted optionally may phenoxy group {said substituent be a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₁ -C ₃ haloalkyl group (said halogen atom is fluorine atom, chlorine The same or different 1 to 3 halogen atoms selected from the group consisting of atoms and bromine atoms), the same or different selected from the group consisting of cyclopropyl groups and tri (C ₁ -C ₃ alkyl) silicon groups 1 to 2 different substituents. }, The same or different 1 or 2 substituents selected from the group consisting of a cyclopropyl group and a tri (C ₁ -C ₃ alkyl) silicon group. } Or a tri (C ₁ -C ₃ alkyl) silicon group,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom or an optionally substituted C ₁ -C ₄ alkyl group (the substituent is a fluorine atom, chlorine The same or different 1 to 3 substituents selected from the group consisting of an atom and a bromine atom, or a C _{3 to} C ₄ cycloalkyl group.), An optionally substituted C _{3 to} C ₅ cycloalkyl group (said substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl group, C ₃ -C ₄ has the same or different selected from the group consisting of cycloalkyl group and C ₁ -C ₃ alkoxy groups 1 to 3 substituents), a C _{6 to} C ₇ bicycloalkyl group, an optionally substituted phenyl group (the substituent is a fluorine atom, a chlorine atom, a bromine atom, a C _{1 to} C ₃ alkyl group). groups or C ₁ -C ₃ haloalkyl group (said halogen atom, The same or different 1 to 3 halogen atoms selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom. }, An optionally substituted 5- to 6-membered heterocyclic group {the heterocyclic ring contains one nitrogen atom, oxygen atom or sulfur atom in the ring, and further contains 1 to 2 nitrogen atoms may contain, the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C ₃ alkyl and C ₁ -C ₃ haloalkyl group (said halogen atom is a fluorine atom, a chlorine atom and a bromine atom The same or different 1 to 3 halogen atoms selected from the group consisting of: 1 to 2 identical or different substituents selected from the group consisting of: }, Nitro group, C ₁ -C ₃ alkoxy groups, C ₁ -C ₃ haloalkoxy group (said halogen atom is a fluorine atom, 1-3 was selected same or different from the group consisting of chlorine and bromine of a halogen atom.), or an optionally substituted phenoxy group (the substituent is a fluorine atom, a chlorine atom, pyridazinyloxy substituted by any of a bromine atom and C ₁ -C ₃ alkoxy groups Or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form a group of the formula: —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH═CH—CH═CH—, —OCH ₂ CH ₂ —, —OCH = CH -, - OCH = C ( CH 3) -, - SCH = CH -, - N = CH-CH = _{CH -, - OCH 2 O -} , - OCH 2 CH 2 O-,

The manufacturing method of Claim 1 or 2 which is a compound which forms group represented by these. In the 3-phenoxy-4-pyridazinol derivative (I),
R ¹ is a chlorine atom, a bromine atom or a trifluoromethyl group,
R ² is a hydrogen atom, a halogen atom, a methyl group or a trimethylsilyl group,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, or an optionally substituted C ₁ -C ₄ alkyl group (the number of the substituent is 1 to 3 Or a C ₃ -C ₄ cycloalkyl group which may be substituted (the substituent is a fluorine atom, a chlorine atom, a bromine atom, C ₁ -C). _The same 1-2 substituents selected from the group consisting of ₂ alkyl groups, cyclopropyl groups and C ₁ -C ₂ alkoxy groups.), Nitro groups, C ₁ -C ₃ alkoxy groups or trifluoromethoxy groups Or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are combined together to form the formula —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH. ₂ CH ₂ —, —OCH ₂ CH ₂ —, —OCH═CH— or

The production method according to claim 1 or 2, wherein R ³ is a compound that is not a hydrogen atom. In the 3-phenoxy-4-pyridazinol derivative (I),
R ¹ is a chlorine atom or a bromine atom,
R ² is a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₃ alkyl group, an optionally substituted C ₃ -C ₄ cycloalkyl group ( the substituents are identical one to two substituents selected from the group consisting of a chlorine atom and C ₁ -C ₂ alkyl group.) or a C ₁ -C ₂ alkoxy group, or, R ³ , R ⁴ , R ⁵ , R ^6, and R ⁷ together form a group represented by the formula —CH ₂ CH ₂ CH ₂ — or —OCH═CH—, However, R ³ is a compound not a hydrogen atom, a manufacturing method according to claim 1 or 2. In the 3-phenoxy-4-pyridazinol derivative (I),
R ¹ is a chlorine atom,
R ² is a hydrogen atom,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a halogen atom, a methyl group, an ethyl group, an isopropyl group, an optionally substituted cyclopropyl group (the substituent is 2 chlorine atoms) or a methoxy group, or two of R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are taken together to form the formula —CH ₂ CH ₂ CH ₂ - to form a group represented by the proviso, R ³ is a compound not a hydrogen atom, a manufacturing method according to claim 1 or 2. In the 3-phenoxy-4-pyridazinol derivative (I),
R ¹ is a chlorine atom,
R ² is a hydrogen atom,
R ³ is a chlorine atom, bromine atom, methyl group, ethyl group, isopropyl group or cyclopropyl group, R ⁴ is a hydrogen atom or a methyl group, or R ³ and R ⁴ are combined together And a group represented by the formula —CH ₂ CH ₂ CH ₂ —, wherein R ⁵ is a hydrogen atom, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrogen atom, a chlorine atom or The manufacturing method of Claim 1 or 2 which is a compound which is a methyl group.